Production of metathesis products by amorphous polymer segment interchange

ABSTRACT

A cross-metathesized product mixture is prepared by contacting a metathesis catalyst under metathesis conditions with a composition comprising two or more chemically distinguishable ethylenically unsaturated polymers, at least one of said ethylenically unsaturated polymers (first polymer) having from 0.001 to 50 mole percent unsaturation and at least one other of said ethylenically unsaturated polymers (second polymer) being an amorphous polymer having a Tg less than 0° C. and having from 0.001 to 5 mole percent unsaturation.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a 371 filing of International Patent Application No.PCT/US2007/018624, filed Aug. 23, 2007, which claims the benefit of U.S.Provisional Patent Application Ser. No. 60/840,325, filed Aug. 25, 2006.

BACKGROUND OF THE INVENTION

In one aspect, the present invention relates to a process for preparingblock copolymers by metathesis of two or more polymers containingethylenic unsaturation. In another aspect, this invention relates toblock copolymers prepared by the metathesis process of this invention.Numerous olefin metathesis processes are previously known in the art. Ingeneral, olefin metathesis involves catalytic cleavage of one or moreolefins at a point of unsaturation and recombination of the resultingcleavage products to form different olefin containing reaction products.Often, low molecular weight olefins and cyclic olefins are employed asreagents in the foregoing reaction mixtures in order to provide lowviscosity reaction mixtures, well defined reaction products, reducedpolymer product molecular weight, and/or mixtures suitable for reactioninjection molding (RIM) compositions. Examples of the foregoingprocesses are disclosed in U.S. Pat. Nos. 5,731,383, 4,994,535,4,049,616, 3,891,816, 3,692,872, and elsewhere.

Metathesis involving polymeric olefins is also known. In Macromol., 33,1494-1496 (2000), solid polymers were depolymerized by surface contactwith a metathesis catalyst. Reaction products of polymer metathesis caninclude random or block copolymers, functionalized polymers obtainedthrough functionalization of resulting terminal unsaturation, ringopened metathesis products, and even cross-linked solids. Metathesis oftwo or more olefins is referred to as a “cross-metathesis”. Examples ofsuch processes are disclosed by U.S. Pat. Nos. 6,867,274, 6,410,110,5,603,985, 5,559,190, 5,446,102, 4,049,616, and other references.Suitable unsaturated polymers for the foregoing processes include dienehomopolymers and copolymers or partially hydrogenated derivativesthereof. Use of cyclic olefins can result in the formation of polymershaving narrow molecular weight distributions. For example, preparationsof linear polyethylene and poly(ethylidene-norbornene)/polycyclopentenediblock copolymers by ring opening metathesis of polycyclopentene orsequential polymerization of mixtures of ethylidene-norbornene andpolycyclopentene were disclosed in Macromol., 33(25), 9215-9221 (2000).

In U.S. Pat. Nos. 3,692,872, 3,891,816 and 4,010,224 graft and blockcopolymers and interpolymers were prepared by metathesis of two polymerscontaining olefinic unsaturation, such as polybutadiene or polyisoprene.Monomers such as cyclooctene or dimers such ascyclooctadiene-cyclopentadiene dimer could be included in thepolymerization as well. Similar processes involving the cross-metathesisof polybutadiene with polycyclooctene or polycyclododecene as well asgrafting of EPDM polymers via metathesis were disclosed in DE 2,131,355and DE 2,242,794. In the former process, “thermoplastic properties wereimparted to the elastomer”. A summary of the work appeared in J. Mol.Catal., 15, 3-19 (1982).

Similarly, in U.S. Pat. Nos. 3,692,872, 3,891,816 and 4,010,224 graftand block copolymers and interpolymers were prepared by metathesis oftwo polymers containing olefinic unsaturation, such as polybutadiene andpolyisoprene. Monomers and dimers such as cyclooctene orcyclooctadiene-cyclopentadiene dimer could be included in thepolymerization as well. Exemplified polymer pairs included partiallypolymerized cements of polycyclooctene and polycyclooctadiene (Ex. I),EPDM/polybutadiene (Ex. II and V), and two EPDM/cyclooctadienecopolymers having differing cyclooctadiene contents (Ex. III).

In Macromol., 36, 9675-96777 (2003) the ethenolysis ofpolypropylene/1,3-butadiene copolymers to prepare polymers havingslightly increased melting temperature for the isotactic polymersegments due to improved packing of shorter chain segments wasdisclosed. In German Democratic Republic patents DD 146,052 and DD146,053, 1,4-cis-polybutadiene and copolymers such as ABS rubber or SBrubber were subjected to metathetic depolymerization optionally in thepresence of a functionalizing agent, especially an unsaturatedcarboxylic acid ester. According to U.S. Pat. No. 7,022,789, theproducts were polydisperse rubbers indicating the presence ofcross-linking due to undesirable quantities of vinyl groups in theproduct.

Disadvantageously, the foregoing known polymeric olefin metathesisproducts are lacking in desirable physical properties due to the factthat at equilibrium, the individual blocks do not differ significantlyfrom one another in chemical properties. For example, segment propertiesof polycyclooctene and polycyclododecene or of polybutadiene andpolyisoprene, are nearly chemically equivalent. Copolymers comprised ofsuch polymer segments do not possess advantaged properties. Conventionalblock copolymers, such as those prepared by anionic polymerizationtechniques readily incorporate dissimilar, immiscible, segments in thesame polymer chain. Because the segments possess different physicalproperties, such as glass transition temperature (Tg), crystallinemelting point (Tm), dielectric constant or solubility parameter theresulting polymers possess enhanced properties. For example, thepresence of crystalline polymer segments having a relatively highmelting point and elastomeric polymer segments within the same polymerchain gives thermoplastic materials having improved elastomeric andmechanical properties, such as high tensile strength, hysteresis, andtear properties.

It would be desirable if there were provided a process for themetathesis of unsaturated polymers that is specifically adapted for theformation of differentiated, commercially valuable copolymer products,having many of the properties of conventional, non-random blockcopolymers. It would further be desirable if the resulting polymerproducts were suitable for use as molding resins, adhesives, sealants,and impact modifiers. Finally, it would be desirable to provide aprocess for converting readily available, inexpensive, unsaturatedpolymers into copolymers having differentiated, commercially valuableproperties.

SUMMARY OF THE INVENTION

According to the present invention there is now provided a process forpreparing a cross-metathesized product mixture comprising contacting ametathesis catalyst under metathesis conditions with a compositioncomprising two or more chemically distinguishable ethylenicallyunsaturated polymers, at least one of said ethylenically unsaturatedpolymers (first polymer) having from 0.001 to 50 mole percentunsaturation and at least one other of said ethylenically unsaturatedpolymers (second polymer) being an amorphous polymer having a Tg lessthan 0° C. and having from 0.001 to 5 mole percent unsaturation, tothereby form the cross-metathesized reaction product.

In another embodiment of the invention, there is provided thecross-metathesized reaction product formed by contacting a metathesiscatalyst under metathesis conditions with a composition comprising twoor more ethylenically unsaturated polymers, at least one of saidethylenically unsaturated polymers (first polymer) having from 0.001 to50 mole percent unsaturation and at least one other of saidethylenically unsaturated polymers (second polymer) being an amorphouspolymer having a Tg less than 0° C. and having from 0.001 to 5 molepercent unsaturation.

Suitable unsaturated polymers employed in the present metathesis arepolymers prepared by addition polymerization, condensationpolymerization, ring opening cycloaddition, or other process orcombination of processes capable of forming polymers containingethylenic unsaturation. At least some of the ethylenic unsaturation inthe reagent polymers, preferably most or substantially all of theunsaturation, is located in the main chain or backbone (internalunsaturation). Such internal ethylenic unsaturation desirably results information of segments in at least one of the unsaturated polymerreagents that are of sufficient length so as to possess an expected Tgor measured Tm of less than 0° C. (alternatively referred tohere-in-after as “soft segments”). Both the reagent polymer and theresulting cross-metathesized polymer product possess said soft segments.

Desirably, the ethylenic content of the second unsaturated polymerreagent is from 0.001 to less than 3 mole percent, more preferably from0.01 to 2 mole percent, even more preferably from 0.1 to 1.0 molepercent. Conversely, the ethylenic content of the first unsaturatedpolymer reagent is desirably at least 10 mole percent, more preferablyat least 15 mole percent, and even more preferably at least 20 molepercent. In certain desirable embodiments, the ethylenic carbon contentof the unsaturated polymer reagents is less than or equal to 40 weightpercent, preferably less than or equal to 35 weight percent. Thequantity of ethylenic unsaturation in the polymer reagents may beadjusted prior to metathesis by partial hydrogenation, in order toattain the desired polymer segment lengths. Further desirably, thesecond reagent polymer is formed by copolymerization of ethylene orpropylene with small quantities of a diene monomer or an alkyne,especially a conjugated diene, and one or more copolymerizablecomonomers, especially one or more α-olefin comonomers. Moreover, thedistribution of diene monomer in this reagent polymer is substantiallyrandom. More preferably, at least 99 percent of Multiple unsaturationsremaining in the polymer, especially at least 99.9 percent thereof, areseparated by at least 4 methylene or substituted methylene units, mostpreferably at least 6 such units. Highly preferably, the secondunsaturated polymer reagent is formed by an addition polymerizationprocess, especially a coordination polymerization process.

Preferably, the second unsaturated polymer reagent contains segmentshaving lengths of greater than 10 atoms, more preferably at least 20,and most preferably at least 40 carbon atoms. It will be appreciated bythe skilled artisan that by using unsaturated polymer reagents withhigher unsaturation content, shorter polymer blocks in the resultingpolymeric product result. Desirably, the soft segment containingpolymers have Tg of less than −25° C., even more preferably less than−40° C.

Examples of unsaturated soft segment containing polymers for use asreagents or components of the reaction mixture herein include randomcopolymers of ethylene with one or more C₃₋₂₀ olefin monomers and one ormore diolefins; random copolymers of ethylene with one or more C₃₋₂₀olefin monomers and one or more alkynes; random copolymers of ethylenewith one or more C₃₋₂₀ olefin monomers, one or more diolefins, and oneor more alkynes; condensation polymers formed by condensation of two ormore condensable monomers at least one of which comprises ethylenicunsaturation; free radically polymerized homopolymers and copolymers ofat least one conjugated diene and a copolymerizable comonomer, partiallyhydrogenated derivatives of the foregoing, and partially hydrogenatedconjugated diene homopolymers, so long as the polymers possess thepreviously identified unsaturation content and Tg value.

Most preferred second polymer reagents are substantially randomcopolymers of ethylene with propylene, 1-butene, 1-hexene, or 1-octeneand one or more conjugated dienes, containing up to 5 percent,preferably up to 3 mole percent, more preferably up to 1 mole percentpolymerized diene, and partially hydrogenated derivatives thereof.Preferred conjugated dienes are especially butadiene, isoprene,2-chloro-1,3-butadiene, and 2-fluoro-1,3-butadiene. Examples includecopolymers of ethylene, propylene, and one or more of butadiene,isoprene, 2-chloro-1,3-butadiene, or 2-fluoro-1,3-butadiene, copolymersof ethylene, 1-hexene and one or more of butadiene, isoprene,2-chloro-1,3-butadiene, or 2-fluoro-1,3-butadiene; or copolymers ofethylene, 1-octene, and one or more of butadiene, isoprene,2-chloro-1,3-butadiene, or 2-fluoro-1,3-butadiene. Because techniquesfor hydrogenation of polymers are relatively expensive and inconvenientdue to the fact that the polymer normally needs to be dissolved orliquefied, preferred reagent polymers are those possessing limitedquantities of polymerized diene and not hydrogenated derivatives ofdiene homopolymers or copolymers. Such copolymers uniquely and desirablypossess inherently low vinyl contents, leading to highly linearcross-metathesized reaction products.

Any remaining unsaturated polymer reagent(s) (in addition to the firstand second polymers) employed in the cross-metathesis may be of theforegoing types, or an ethylenically unsaturated polymer having anexpected Tg or measured Tm value greater than 100° C. (hard segmentcontaining polymer) or a homopolymer or copolymer of one or more dienes,especially polymers of one or more conjugated dienes, prepared by freeradical polymerization techniques. Preferred polymers includepolybutadiene, polyisoprene, poly(2-chloro-1,3-butadiene),acrylonitrile/butadiene copolymers, and poly(2-fluoro-1,3-butadiene.

In one embodiment of the invention, at least one of the unsaturatedpolymer reagents is incompatible with at least one other unsaturatedpolymer reagent and the resulting cross-metathesized product iscompatibilized due to formation of a quantity of the presentcross-metathesized product. Examples of unsaturated polymers thatcommonly are incompatible with one another include polar groupcontaining polymers and non-polar polymers. Evidence of improvedcompatibility of compositions according to the invention includedecreased crystallite size, improved clarity, increased impact strength,improved ductility, and/or increased tensile properties of the resultingcross-metathesized polymer product compared to the initial polymermixture before undergoing metathesis.

The preparation, especially in the melt, of a compatibilized productmixture according to the foregoing embodiment of the invention is oftenexpedited by addition to the initially incompatible polymers of a smallquantity of preformed cross-metathesized copolymer, prepared by solutiontechniques, by copolymerization of representative monomers, or obtainedfrom previous operation of the present invention. This initial “seed” ofpreviously formed compatibilizer can substantially reduce the timerequired to achieve formation of a homogeneous cross-metathesizedproduct. Additionally, an olefin, especially ethylene, can be employedto reduce the viscosity of the reaction mixture, especially in theinitial stages of the process. It can be removed at later stages of thereaction by heating the reaction mixture in the absence of added olefinbut in the presence of the metathesis catalyst, optionally under reducedpressure. Stoichiometric amounts of added olefin, such as a cyclicolefin or ethylene, can also be used to adjust the molecular weight ofthe resulting cross-metathesized product mixture.

Additional desirable embodiments of the present invention includecross-metathesis processes wherein at least one of the reagent polymersis (are) amorphous having from 0.001 to 5 mole percent unsaturation andone other reagent polymer is (are) crystallizable, also having from0.001 to 5 mole percent unsaturation. Preferably the difference betweenexpected Tg for the amorphous polymer and the measured Tm for thecrystallizable polymer is at least 40° C., more preferably at least 80°C., and most preferably at least 100° C. Highly desirably, Tm for thecrystallizable polymer is higher than the expected Tg for the amorphouspolymer. Even more preferably, the crystallizable polymer and/or thesegments thereof have a crystalline melting point (Tm) of at least 100°C., highly preferably at least 105° C., and most preferably at least120° C. Further desirably, the heat of fusion associated with themelting point of the crystalline polymer or segments thereof is at least20 J/g, preferably at least 40 J/g, more preferably at least 50 J/g, asdetermined by DSC analysis. Included are polymers in which crystallinityis induced or enhanced by the use of nucleating agents, thermalannealing, and/or strain.

With respect to all of the foregoing polymers or polymeric compositionsconstituting embodiments of the invention, processes for forming thesame and methods of using them as molding resins, adhesives, andcomponents of blended compositions are also included within the presentinvention.

In the embodiments of the invention wherein the second polymercontaining soft segments is formed by polymerization of ethylene, one ormore C₃₋₂₀ α-olefins, and a conjugated diene or alkyne, such polymer isinherently low in pendant vinyl functional groups, thereby obviating theneed for hydrogenation to reduce the level of unsaturation. Theresulting metathesis products inherently possess high α,ω-unsaturationand are highly linear. Through selection of appropriate coordinationcatalysts and reaction conditions, the pendant vinyl functionality insuch amorphous copolymers may be reduced to as low as 5 percent or less,even 2 percent or less, and even 1 percent or less of the totalethylenic groups, and with hydrogenation, even lower. The resultingmetathesis products and functionalized derivatives thereof accordinglyhave a significantly reduced proclivity to form cross-links or pendantbranches. Desirably, functionalities from 1.9 to 2.5, preferably from2.0 to 2.2 are attainable.

In addition, because the diene remnant in the soft segment containingcopolymer reagents is not necessarily employed for purposes of impartingelastomeric properties to the resulting product, and desirably isn't soemployed, a wide variety of polymer properties and combinations ofproperties can be introduced into the resulting products. Especiallypreferred cross-metathesis products are formed by metathesis ofpolybutadiene or poly(2-chloro-1,3-butadiene) withethylene/1-octene/diene copolymers comprising no more than 5, preferablyno more than 3, more preferably no more than 2, and most preferably nomore than 1 mole percent butadiene, isoprene, or 2-chloro-1,3-butadiene.

The products are usefully employed in the manufacture of adhesives, asmolding resins and adhesive films for multi-layer laminations such asbags, pouches and laminated feed stock and as compatibilizers used inthe formation of blends of polyethylene or other olefin polymers.

DRAWINGS

FIG. 1 illustrates SAXS plots at three temperatures of a composition ofthis invention prepared as described in Example 1.

FIG. 2 illustrates SAXS plots at three temperatures of a controlcomposition prepared as described in Comparative Experiment A.

FIG. 3 (lower graph) illustrates an ¹H NMR spectrum of a composition ofthis invention prepared as described in Example 2.

FIG. 3 (upper graph) illustrates an ¹H NMR spectrum of a controlcomposition prepared as described in Comparative Experiment B.

FIG. 4 illustrates a TEM scan of a composition of this inventionprepared as described in Example 3.

FIG. 5 illustrates SAXS plots at three temperatures of a composition ofthis invention prepared as described in Example 3.

FIG. 6 illustrates a CRYSTAF graph for a composition of this inventionprepared as described in Example 4.

FIG. 7 illustrates a CRYSTAF graph for a control composition prepared asdescribed in Comparative Experiment C.

DETAILED DESCRIPTION OF THE INVENTION

All references to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 2003. Also, any references to a Group or Groups shall be tothe Group or Groups reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups disclosed in, Nomenclatureof Inorganic Chemistry: Recommendations 1990, G. J. Leigh, Editor,Blackwell Scientific Publications (1990). Unless stated to the contrary,implicit from the context, or customary in the art, all parts andpercents are based on weight. For purposes of United States patentpractice, the contents of any patent, patent application, or publicationreferenced herein are hereby incorporated by reference in their entirety(or the equivalent US version thereof is so incorporated by reference)especially with respect to the disclosure of synthetic techniques,definitions (to the extent not inconsistent with any definitionsprovided herein) and general knowledge in the art.

The term “comprising” and derivatives thereof is not intended to excludethe presence of any additional component, step or procedure, whether ornot the same is disclosed herein. In order to avoid any doubt, allcompositions claimed herein through use of the term “comprising” mayinclude any additional additive, adjuvant, or compound whether polymericor otherwise, unless stated to the contrary. In contrast, the term,“consisting essentially of” excludes from the scope of any succeedingrecitation any other component, step or procedure, excepting those thatare not essential to operability. The term “consisting of” excludes anycomponent, step or procedure not specifically delineated or listed. Theterm “or”, unless stated otherwise, refers to the listed membersindividually as well as in any combination.

As used herein with respect to a chemical compound, unless specificallyindicated otherwise, the singular includes all isomeric forms and viceversa (for example, “hexane”, includes all isomers of hexaneindividually or collectively). The terms “compound” and “complex” areused interchangeably herein to refer to organic-, inorganic- andorganometal compounds. The term, “atom” refers to the smallestconstituent of an element regardless of ionic state, that is, whether ornot the same bears a charge or partial charge or is bonded to anotheratom. The term “heteroatom” refers to an atom other than carbon orhydrogen. Preferred heteroatoms include: F, Cl, Br, N, O, P, B, S, Si,Sb, Al, Sn, As, Se and Ge.

The term, “hydrocarbyl” refers to univalent substituents containing onlyhydrogen and carbon atoms, including branched or unbranched, saturatedor unsaturated, cyclic, polycyclic or noncyclic species. Examplesinclude alkyl-, cycloalkyl-, alkenyl-, alkadienyl-, cycloalkenyl-,cycloalkadienyl-, aryl-, and alkynyl-groups. “Substituted hydrocarbyl”refers to a hydrocarbyl group that is substituted with one or morenonhydrocarbyl substituent groups. The term “heterocarbyl” refers togroups containing one or more carbon atoms and one or more heteroatomsand no hydrogen atoms. The bond between the carbon atom and anyheteroatom as well as the bonds between any two heteroatoms, may be asingle or multiple covalent bond or a coordinating or other donativebond. Examples include trichloromethyl-, perfluorophenyl-, cyano- andisocyanato-groups. The terms “heteroatom containing hydrocarbyl” or“heterohydrocarbyl” refer to univalent groups in which at least one atomother than hydrogen or carbon is present along with one or more carbonatoms and one or more hydrogen atoms. Thus, an alkyl group substitutedwith a halo-, heterocycloalkyl-, aryl-substituted heterocycloalkyl-,heteroaryl-, alkyl-substituted heteroaryl-, alkoxy-, aryloxy-,dihydrocarbylboryl-, dihydrocarbylphosphino-, dihydrocarbylamino-,trihydrocarbylsilyl-, hydrocarbylthio-, or hydrocarbylseleno-group iswithin the scope of the term heterohydrocarbyl. Examples of suitableheteroalkyl groups include chloromethyl-, 2-cyanoethyl-, hydroxymethyl-,benzoylmethyl-, (2-pyridyl)methyl-, chlorobenzyl-, andtrifluoromethyl-groups.

As used herein the term “aromatic” refers to a polyatomic, cyclic,conjugated ring system containing (4δ+2) π-electrons, wherein δ is aninteger greater than or equal to 1. The term “fused” as used herein withrespect to a ring system containing two or more polyatomic, cyclic ringsmeans that with respect to at least two rings thereof, at least one pairof adjacent atoms is included in both rings. The term “aryl” refers to amonovalent aromatic substituent which may be a single aromatic ring ormultiple aromatic rings which are fused together, linked covalently, orlinked to a common group such as a methylene or ethylene moiety.Examples of aromatic ring(s) include phenyl, naphthyl, anthracenyl, andbiphenyl, among others.

“Substituted aryl” refers to an aryl group in which one or more hydrogenatoms bound to any carbon is replaced by one or more functional groupssuch as alkyl, alkenyl, substituted alkyl, substituted alkenyl,cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, halo, haloalkyl (for example, CF₃), hydroxy, amino,phosphido, alkoxy, amino, thio, nitro, and both saturated andunsaturated hydrocarbylene groups, including those which are fused tothe aromatic ring(s), linked covalently or linked to a common group suchas a methylene or ethylene moiety. The common linking group may also becarbonyl as in benzophenone-, oxygen as in diphenylether- or nitrogen asin diphenylamine-groups.

“Ethylenic unsaturation” or “ethylenic group” refers to adjacentaliphatic carbon atoms bound together by double bonds (non-aromatic sp²electronic hybridization), preferably of the formula: —CR*═CR*—, or—CR*═CR*₂, where R* independently each occurrence is hydrogen, halo,nitrile, hydrocarbyl, or substituted hydrocarbyl containing up to 20atoms not counting hydrogen. Percent ethylenic unsaturation as usedherein is calculated based on total carbon-carbon bond content of thepolymer. The term “ethylenic carbon content” refers to the percent oftotal polymer weight due to such double bonded carbon atoms. Forpurposes of clarity, the ethylenic carbon contents of perfectlyunsaturated polybutadiene, polyisoprene and poly(2-chloro-1,3-butadiene)polymers are 42, 34 and 26 weight percent respectively. The term“pendant” refers to groups or substituents attached to secondary ortertiary substituted carbons of the polymer. The term “terminal” refersto groups or substituents attached to a primary carbon of the polymer.

The term “polymer” as used herein refers to a macromolecular compoundcomprising multiple repeating units and a molecular weight of at least100, preferably at least 1000. Preferably, at least one repeating unitoccurs, consecutively or non-consecutively, 6 or more times, morepreferably 10 or more times, and most preferably 20 or more times onaverage. Molecules containing less than 6 such repeating units onaverage are referred to herein as oligomers. The term includeshomopolymers, copolymers, terpolymers, interpolymers, and so on. Theterm “interpolymer” is used herein interchangeably with the termcopolymer to refer to polymers incorporating in polymerized form atleast two differentiated repeating units, usually obtained from separatecopolymerizable monomers. The least prevalent monomer in the resultingcopolymer or interpolymer is generally referred to by the term“comonomer”.

The term, “segment(s)” refers to portions of an unsaturated polymerhaving a uniform composition and a carbon chain length of at least 12carbons, preferably at least 20 carbons, more preferably at least 30carbons, separated by ethylenic unsaturations or, in the case of apolymer comprising a single terminal unsaturation, terminated by theethylenic unsaturation. Unsaturation occurring within a cyclic moiety,such as an alicyclic or aromatic group does not result in segmentformation. Desirably, the segments in the present copolymers aresubstantially free of internal rings or cyclic moieties. The term“uniform composition” as used herein refers to segments that are derivedfrom the same (co)monomer stream(s), the sequence and stereo-regularityin each segment being governed by the relative reactivity of each(co)monomer. Accordingly, the monomer sequence and stereo-regularity inany two or more segments may range from being essentially identical tobeing substantially different and any degree of variation in betweenthese two extremes.

The term “block copolymer” refers to a polymer having two or moredistinguishable, non-pendant polymer sections (blocks). Desirably, blockcopolymers exhibit the properties of thermoplastic elastomers (TPE)characterized by the presence of “soft” or elastomeric blocks connecting“hard” either crystallizable or glassy blocks in the same polymer. Attemperatures up to the melt temperature or glass transition temperatureof the hard segments, the polymers demonstrate elastomeric character. Attemperatures higher than the crystalline melting point of the hardsegments, the polymers become flowable, exhibiting thermoplasticbehavior.

The term “unsaturated block copolymer” refers to a block copolymer thatcomprises ethylenic unsaturation either between blocks or within one ormore blocks thereof. An unsaturated polymer or an unsaturated blockwithin a block copolymer may comprise one or more segments. The term“amorphous” refers to a polymer, polymer block or polymer segment(collectively referred to here-in-after as polymeric entities) lacking acrystalline melting point. The term “crystalline” refers to a polymericentity possessing a crystalline melting point. The term“semi-crystalline” refers to a polymeric entity possessing a crystallinemelting point which is lower than that of a fully crystalline or morefully crystalline polymer entity of the same chemical composition. Morespecifically, semi-crystalline as used herein, refers to polymerentities possessing crystallinity that is less than 90 percent of themaximum attainable crystallinity for that polymer entity. For theavoidance of doubt, the term crystalline includes semi-crystallinepolymer entities.

The term “backbone” refers to the longest continuous polymeric chain ofa polymer. All other polymer chains are referred to as side chains,branches, or grafted polymer chains. Short chains or short chainbranching refers to branches from the backbone resulting frompolymerization of monomers containing three or more carbons.Polymerization of such monomers containing two or more ethylenicunsaturations can result in the formation of unsaturated branches(pendant unsaturation) in the resulting polymer. Metathesis of polymerscontaining such unsaturated branches can result in formation of “comb”type block copolymers, that is, polymers having multiple polymer chainspendant from a central backbone chain. Alternatively, the resultingpolymer product may be cross-linked.

As used herein, the term “chemically distinguishable” refers topolymeric entities containing an identifiable chemical property orcharacteristic that allows the polymer, block or segment to bedistinguished from another polymer, block or segment. Specificallyexcluded are polymeric entities differing from one another only bymolecular weight or molecular weight distribution such as products thatmay be formed upon metathesis of a single unsaturated polymer. Examplesof chemically distinguishable polymeric entities include those differingin composition, tacticity, density, crystallinity, crystallite size,crystalline melt point, glass transition temperature, dielectricconstant, solubility parameter, interaction parameter (chi). Theforegoing values may be either expected or actually measured. Thepresence of chemically distinguishable polymer entities is readilydetermined by standard analytic techniques, such as identifiable meltpoint, by NMR techniques, IR analysis for polar group containingpolymers, CRYSTAF, ATREF, TREF, or by other methods. Preferred,chemically distinguishable polymer blocks in the present meta-blockcopolymers are those characterized by a difference in crystallinemelting point, polarity (χ), tacticity (rrr or mmm triad), expectedglass transition temperature (Tg), interaction parameter (chi), orexpected solubility parameter.

The chemical properties of a polymer segment herein may be determined byethenolysis of the unsaturated polymer according to known procedures,and analysis of the residual segment properties by standard analyticaltechniques. Separation of differing segments by elutriation,chromatography, or other fractionation technique may be necessary priorto analysis.

Identification of monomer and comonomer, comonomer amount, unsaturationlevels, branching and tacticity in polymeric entities in the presentpolymer reagents and products may be accomplished using NMR techniquessuch as those disclosed in, NMR and Macromolecules: sequence, dynamicand domain structure, James C. Randall, ed.; ACS Symposium Series, 247;American Chemical Society, Washington, D.C. (1984) (here-in-after,Randall).

Polymer properties herein may be characterized by actual values, thatis, measured or calculated values based on samples or expectedproperties. The term “expected” when used in reference to the propertiesof polymer entities are those properties predicted by the method ofinfinite molecular weight, room temperature (25° C.), atactic, polymercalculation disclosed in Jozef Bicerano, Prediction of PolymerProperties, 2nd ed., Marcel Dekker, Inc., New York (here-in-after,Bicerano). The technique is also incorporated into software, includingSYNTHIA™, available from Molecular Simulations Inc., a subsidiary ofPharmacopeia, Inc. The expected properties of certain representativepolymers calculated according to the Bicerano technique are shown inTable 1.

TABLE 1 Calculated Expected Polymer Properties Repeat RefractiveDielectric Glass Solubility Unit Index Constant Transition, ParameterPolymer Formula (n) (∈) Tg (° C.) δ₂((J/cc){circumflex over ( )}½)polyethylene CH₂ 1.4648 2.33 −86 16.8 polypropylene C₃H₆ 1.4713 2.26 −3816.1 poly(1-butene) C₄H₈ 2.28 −57 16.3 poly(1-hexene) C₆H₁₂ 1.466 2.30−77 16.5 poly(1-octene) C₈H₁₆ 1.466 2.31 −86 16.6 polyisobutylene C₄H₈1.4795 2.22 −83 15.4 polystyrene C₈H₈ 1.6037 2.57 106 19.5polychloroprene C₄H₅Cl 1.5673 −36 19.5 poly(1,2-butadiene) C₄H₆ 1.505513 16.8 poly(1,4-butadiene) C₄H₆ 1.5188 2.32 −99 17.7 polyisoprene C₅H₈1.5159 2.28 −72 17.2 polycyclooctene (ROMP)* C₈H₁₄ 1.4918 2.32 −90 17.3polycyclodecene (ROMP)* C₁₀H₁₈ 1.4864 2.32 −88 17.2 polycyclododecene(ROMP)* C₁₂H₂₂ 1.4828 2.32 −87 17.1 poly(methyl methacrylate) C₅H₇O₂1.4846 3.07 84 17.7 poly(acrylonitrile) C₃H₃N 1.5425 3.99 91 24.6poly(vinyl chloride) C₂H₃Cl 1.5560 2.93 20 19.4 poly(vinylidenechloride) C₂H₂Cl₂ 1.6080 2.86 21.0 bisphenol-A polycarbonate C₁₀H₁₄O₃1.5870 2.90 146 19.3 poly(ethylene terephthalate) C₁₀H₈O₄ 1.5558 3.28100 19.8 poly(ε-caprolactam) C₆H₁₁ON 1.5130 3.47 57 25.1poly(ε-caprolactone) C₆H₁₀O₂ 1.475 2.91 −44 17.8 polyoxyethylene C₂H₄O1.4648 2.77 −68 19.1 polyoxymethylene CH₂O 1.465 3.11 −60 20.6 *ROMPmeans ring opening metathesis polymerization

The term “elastomeric” refers to polymeric entities having Tg less than25° C., preferably less than 0° C., and elastic recovery of at least 90percent when tested according to ASTM D-1708 at 21° C. Crystallinemelting point (Tm) refers to the peak melting point determined by DSCaccording to ASTM D-3418 test method.

The unsaturated amorphous polymer reagents are desirably prepared byaddition polymerization of ethylene, one or more C₃₋₈ α-olefincomonomers and a diene, suitably employing a Ziegler/Natta, metallocene,post-metallocene, or other coordination polymerization catalyst,suitable processes for preparation of which are disclosed in more detailhere-in-after. By the term “Ziegler/Natta polymerization catalyst” ismeant a catalyst composition suited for polymerization of olefinscomprising an organometallic compound in which the metal is from groups2, 12 or 13 of the Periodic Table of the Elements in combination with atleast one other compound, especially a halide, oxide or oxyhalide, of ametal selected from groups 4, 5 or 6 of the Periodic Table of theElements.

Due to the relative low unsaturation content of the present soft segmentcontaining copolymer reagents, the segments participating in the presentcross-metathesis desirably have a segment length, or SL, expressed asthe average number of monomeric repeating units, from 20 to 1000,preferably from 40 to 100, which corresponds to copolymers containingfrom about 0.1 to 5 mole percent polymerized diene, preferably from 1 to2.5 mole percent diene. Further desirably, the soft segments present inthe resulting metathesis product are amorphous.

In a preferred embodiment, one unsaturated polymeric reagent is acopolymer of butadiene ethylene and 1-octene, containing from 2 to 10mole percent 1-octene or a copolymer of butadiene, propylene andethylene, containing from 2 to 65 mole percent ethylene, thereby formingaliphatic polymer segments that are amorphous. The other polymericreagent desirably is polybutadiene, polyisoprene,poly(2-chloro-1,3-butadiene), or poly(2-fluoro-1,3-butadiene). Theresulting cross-metathesized polymer product comprises randomcombinations of soft segments from both polymer reagents in the samepolymer, thereby producing a compatibilized blend of the two polymers.For the purposes of this invention, the term “random” refers to aproperty or outcome that follows and/or arises from no describabledeterministic pattern. Metathesis processes are random, in that whichethylenic bonds in an unsaturated polymer cleave and how the resultingmolecular fragments recombine to form new ethylenic bonds are notpredictable and do not follow predetermined rules. It is noted that suchprocesses lead to compositions having a random distribution of polymersegments, and consequentially, a random distribution of polymer blocks.

The amount of ethylenic unsaturation in the reagent polymers can bedetermined by any suitable technique, such as iodine monochloridetitration (IC1), NMR analysis or other technique. When appropriate, acombination of these techniques can be used. IC1 titration is a wellknown technique for determining the level of carbon-carbon unsaturationin a wide variety of polymers wherein iodine monochloride is used toreact with any unsaturations present in the polymer. The method does notdistinguish between internal and terminal or vinyl unsaturation.

NMR spectroscopic analysis has particular utility for use withhomopolymers and copolymers of conjugated dienes, due to the fact thatthe amount of internal unsaturation in the polymers (resulting from1,4-addition of the diene) as opposed to vinyl unsaturation (resultingfrom 1,2-addition of the diene) may be determined using this technique.NMR techniques of polymer analysis include especially those of Randall.

Preferred combinations of unsaturated polymer reagents for use hereinare those containing one or more amorphous segments, especially segmentsthat are highly branched ethylene/1-octene copolymers, and at least oneother unsaturated polymer selected from polybutadiene orpoly(2-chloro-1,3-butadiene). Highly desirably, only two unsaturatedpolymers are employed.

Suitable unsaturated polymers for use herein preferably containnon-terminal ethylenic unsaturation in the polymer backbone or in one ormore branches thereof. Terminal or vinyl unsaturation may also bepresent, without departing from the scope of the present invention, solong as some non-terminal unsaturation is present in at least one of theunsaturated polymer reagents. Ethylenic unsaturation is provided by thediene, especially butadiene, present in an amount to provide, afterpolymerization, the desired level of non-terminal ethylenicunsaturation(s) per molecule.

Additional suitable polymers include those containing functionality,including hydroxyl, acid, especially carboxylic acid, ester, especiallycarboxylic acid ester, amine, halide, nitrile, anhydride, or thiolfunctionality. Generally, the presence of polar functional groups suchas the foregoing, may require the use of metathesis catalysts that arestable and unaffected. Suitable catalysts include homogeneous rutheniumcatalysts including first-generation Grubbs catalysts, exemplified bybis(tricyclohexylphosphine)-benzylidene ruthenium dichloride, andsecond-generation Grubbs catalysts, exemplified bytricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidene]rutheniumdichloride. “First-generation and second-generation Grubbs catalysts,”named for their principle inventor Robert H. Grubbs, are disclosed in WO96/04289, WO 02/083742, and elsewhere. First-generation andsecond-generation Grubbs catalysts tend to be relatively toleranttowards air, moisture, and a wide array of polar functional groups, suchas acid and ester functionalities.

The unsaturated reagent polymers may be readily prepared using standardpolymerization techniques, such as by polymerizing an olefin mixturecomprising one or more olefins in combination with at least oneconjugated or non-conjugated diene using free radical-, addition-, ringopening-, anionic-, cationic-, condensation, or metathesispolymerization techniques. The method by which the unsaturated reagentpolymer is produced may affect the resulting metathesis product. Forexample, larger length blocks will generally result where at least oneof the reagent polymers is a simple diblock or triblock copolymerprepared, for example, by anionic polymerization of an olefin and aconjugated diene. More detailed description of the various methods ofpreparing the unsaturated polymer reagents follows.

A. Free Radical Polymerization

Free-radical polymerization of comonomers is amenable to use with largenumbers of comonomers to produce a wide variety of unsaturated polymerscontaining amorphous or soft blocks. Free-radical polymerization is alsocompatible with polar and non-polar monomers, and the resulting polymersmay be subjected to grafting with additional functionalized polymersegments. The final polymer may be hydrogenated to reduce the level ofunsaturation and/or eliminate terminal unsaturation, if desired.Suitable techniques include free-radical copolymerization of one or morecopolymerizable monomers with a diene and/or an ethynyl compound, suchas an acetylene derivative, and optionally grafting, to form linear orbranched polymers with pendant and/or backbone unsaturations as well aspolymerization under free radical polymerization conditions of one ormore monomers and optionally grafting, further optionally involvingtreatment at high temperatures, dehydrogenation, dehalohydrogenation orother procedure to increase unsaturation.

Monomers suitable for use in free radical polymerization includepractically any ethylenically unsaturated monomer. Examples of suitablemonomers and details regarding such processes are found in “PolymerHandbook”, 4^(th) Ed, Brandrup, Immergut, and Grulke, Eds., Wiley, 1999;and “Copolymerization”, G. E. Ham, Ed., High Polymers, Vol. XVIII,Interscience, 1964.

Preferred monomers suitably polymerized by free radical polymerizationtechniques include aliphatic and aromatic α-olefins and substitutedolefins, conjugated and non-conjugated dienes, and cyclic olefins andpolyolefins. Examples include: ethylene, propylene, 1-butene, 1-hexene,1-octene, 4-methyl-1-pentene, acrylonitrile, methylmethacrylate,butylacrylate, styrene, vinylcyclohexane, α-methylstyrene,p-vinyltoluene, vinyl chloride, vinylidene chloride, vinylidenefluoride, tetrafluoroethylene, 1,3-butadiene, isoprene,2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene,1,4-hexadiene, 1,5-hexadiene, 2,4-hexadiene,2-methyl-3-ethyl-1,3-butadiene, 3-methyl-1,3-pentadiene,2-methyl-3-ethyl-1,3-pentadiene, 2-ethyl-1,3-pentadiene,3-methyl-1,3-heptadiene, 3-octadiene, 3-butyl-1,3-octadiene,3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-pentadiene,4,5-diethyl-1,3-octadiene, 2-phenyl-1,3-butadiene,2,3-diethyl-1,3-butadiene, 2,3-di-n-propyl-1,3-butadiene,2-methyl-3-isopropyl-1,3-butadiene, 2-chloro-1,3-butadiene,2-fluoro-1,3-butadiene, 2-methoxy-1,3-butadiene,2-ethoxy-3-ethyl-1,3-butadiene, 2-ethoxy-3-methyl-1,3-hexadiene,decadiene, divinylbenzene, cyclohexene, vinylcyclohexene,benzocyclobutene, norbornene, norbornadiene, dicyclopentadiene,ethylidene norbornene and mixtures thereof.

B. Addition Polymerization

Addition polymerization processes, such as transition metal catalyzedpolymerizations more fully disclosed here-in-after, are compatible witha large number of monomers, normally excluding unprotected polar groupcontaining monomers. Certain monomers can yield crystalline polymerswith high melting points or polymers with very low glass transitiontemperatures. Polymers made by polymerizing one or more additionpolymerizable monomers along with a diene, preferably a conjugatedalkadiene, especially 1,4-butadiene, and/or an alkyne compound,especially an acetylene derivative, form branched or linear polymerswith pendant and/or backbone unsaturation(s). Additionally, chain endunsaturation may result due to beta-hydride elimination and/or a smallquantity of backbone unsaturation(s) may result from a randomspontaneous dehydrogenation during the polymerization process. Parentunsaturated polymers made by addition polymerization processes can bepartially hydrogenated to limit the amount of ethylenic unsaturation tothe afore-mentioned preferred range and/or control the type ofunsaturation, for example, by preferentially hydrogenating terminaland/or pendant unsaturation.

A partial list of monomers suitably polymerized by additionpolymerization techniques includes aliphatic and aromatic α-olefins andsubstituted olefins, conjugated and non-conjugated dienes, and cyclicolefins and polyolefins. Examples include: ethylene, propylene,1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, acrylonitrile,methylmethacrylate, butylacrylate, styrene, vinylcyclohexane,α-methylstyrene, p-vinyltoluene, 1,3-butadiene, isoprene,2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene,1,4-hexadiene, 1,5-hexadiene, 2,4-hexadiene,2-methyl-3-ethyl-1,3-butadiene, 3-methyl-1,3-pentadiene,2-methyl-3-ethyl-1,3-pentadiene, 2-ethyl-1,3-pentadiene,3-methyl-1,3-heptadiene, 3-octadiene, 3-butyl-1,3-octadiene,3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-pentadiene,4,5-diethyl-1,3-octadiene, 2-phenyl-1,3-butadiene,2,3-diethyl-1,3-butadiene, 2,3-di-n-propyl-1,3-butadiene,2-methyl-3-isopropyl-1,3-butadiene, 2-chloro-1,3-butadiene,2-fluoro-1,3-butadiene, 2-methoxy-1,3-butadiene,2-ethoxy-3-ethyl-1,3-butadiene, 2-ethoxy-3-methyl-1,3-hexadiene,decadiene, divinylbenzene, cyclohexene, vinylcyclohexene,benzocyclo-butene, norbornene, norbornadiene, dicyclopentadiene,ethylidene norbornene, and mixtures thereof.

C. Anionic Polymerization

Anionic polymerization is often very useful in making block copolymerscontaining ethylenic unsaturation, such as by consecutive monomeraddition schemes or coupling processes. Conjugated dienes ormutifunctional monomers are used to introduce backbone and/or pendantunsaturation in the polymers. Polymers, especially, those containingbutadiene or isoprene, may be partially hydrogenated to control theamount and type of unsaturation. Suitable monomers for polymerizationunder anionic polymerization conditions include:

ethylene, styrene, α-methylstyrene, and p-vinyltoluene,

conjugated dienes such as 1,3-butadiene, isoprene,2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,5-hexadiene,2,4-hexadiene, 1,3-hexadiene, 2-methyl-3-ethyl-1,3-butadiene,3-methyl-1,3-pentadiene, 2-methyl-3-ethyl-1,3-pentadiene,2-ethyl-1,3-pentadiene, 3-methyl-1,3-heptadiene, 3-octadiene,3-butyl-1,3-octadiene, 3,4-dimethyl-1,3-hexadiene,3-n-propyl-1,3-pentadiene, 4,5-diethyl-1,3-octadiene,2-phenyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene,2,3-di-n-propyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene,

divinylbenzene and divinyltoluene,

methylmethacrylate, cyanoacrylate, and butylacrylate,

acrylonitrile.

D. Ring Opening Polymerization

Ring-opening polymerizations can result in polymers and copolymers withbackbone or pendant unsaturation if functional comonomers are employed.Unsaturations can also be incorporated into the polymer through thechoice of initiating group, such as unsaturated alcohols. A partial listof suitable compounds subject to ring opening polymerization includes:

ethylene oxide, propylene oxide, tetrahydrofuran, and trioxane,

lactams, such as caprolactam,

cyclic thioethers,

epichlorohydrin and derivatives thereof,

oxepans and oxetanes,

lactones,

lactides,

cyclic anhydrides, and

cyclic amines.

E. Metathesis Polymerization

Metathesis of unsaturated monomers or monomer mixtures can be used toproduce one or all unsaturated polymers for use according to the presentinvention. Such polymers and copolymers naturally contain ethylenicunsaturation along the polymer backbone. Additional pendant double bondscan be introduced through use of multifunctional monomers. A partiallist of suitable monomers for use in such a metathesis polymerizationincludes:

acyclic dienes, such as 1,3-butadiene, isoprene,2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,5-hexadiene,2,4-hexadiene, 1,3-hexadiene, 2-methyl-3-ethyl-1,3-butadiene,3-methyl-1,3-pentadiene, 2-methyl-3-ethyl-1,3-pentadiene,2-ethyl-1,3-pentadiene, 3-methyl-1,3-heptadiene, 3-octadiene,3-butyl-1,3-octadiene, 3,4-dimethyl-1,3-hexadiene,3-n-propyl-1,3-pentadiene, 4,5-diethyl-1,3-octadiene,2-phenyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene,2,3-di-n-propyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene,2-chloro-1,3-butadiene, 2-fluoro-1,3-butadiene, 2-methoxy-1,3-butadiene,2-ethoxy-3-ethyl-1,3-butadiene, and 2-ethoxy-3-methyl-1,3-hexadiene,

cyclic olefins such as cyclopentene, cyclohexene, and cyclooctene,

cyclic dienes such as cyclopentadiene, dicyclopentadiene, ethylidenenorbornene, norbornene, norbornadiene, and cyclooctadiene.

F. Condensation or Step-Growth Polymerization

Condensation polymers and copolymers may be produced using co-monomershaving pendant or backbone unsaturation thereby preparing unsaturatedpolymers suitable for use as one or all of the unsaturated polymerreagents of the present metathesis process. In addition, polymerscontaining ester functionality may be exposed to transesterificationwith molecules containing backbone or pendant unsaturation to produceunsaturated polymers suitable for use in the present process. Examplesof compounds suitable for use in such transesterification processes (andthe present invention) include: polyesters, polyanhydrides, polyacetals,polyacrylamide, polyamides, polyurethanes, polyureas, silk fibroin,cellulose, phenol-formaldehyde resins, urea-formaldehyde resins,polysulfides, polysiloxanes, polycarbonates, polyethers, polyimides,polyimines, polysaccharides, and proteins. Preferred condensation orstep-growth polymers for use in the present invention includeethylenically unsaturated polyamides, polycarbonates, polyurethanes andpolyethers.

It is to be understood that while all of the foregoing processes forpreparing unsaturated polymers suitable for use in the present processprovided that the previously disclosed requirements regarding ethylenicunsaturation content and Tg between polymer pairs are observed. Mostpreferred unsaturated soft segment containing polymers for use in thepresent invention are polyolefinic hydrocarbons of relatively uniformcomposition, having polydispersity from about 1.8 to 5.0, prepared byaddition polymerization, especially coordination polymerization, ofethylene, one or more C₃₋₂₀ aliphatic α-olefins, and a conjugated diene,especially butadiene, isoprene or 2-chloro-1,3-butadiene.

Metathesis Process Description

Suitable metathesis conditions for use herein include sequential orsimultaneous contacting, of one or more metathesis catalysts with therespective unsaturated polymer reagents. The metathesis may take placein the liquid phase, such as by use of solvents or in melts of one ormore polymers, or in a solid state process, and does not require thatpolymers be completely miscible or soluble at all times during theprocess. The unsaturated polymer reagents can be synthesized in parallelor series with the present metathesis in one or more bulk, solution,slurry, suspension, gas phase, or other polymerization reactors, eitheras one unit operation of the present process or separately. In oneembodiment, the parent polymers for the present metathesis arecoproduced prior to metathesis, and subjected to the present processprior to recovery or isolation, thereby avoiding the need for remelting,dissolution and/or blending of the unsaturated polymer reagents. Highlydesirably, the temperature and reaction medium are chosen so that atleast one component of the reaction mixture is molten or sufficientlysolubilized to provide a fluid reaction medium.

The molecular weight of the resulting polymer products may range from aslow as 250 g/mole, and as high as 1×10⁷ g/mole. The polydispersity(Mw/Mn) is dependent on the polydispersity and functionality of theparent polymers. Suitable ranges of Mw/Mn for the resulting polymerproducts are from close to 1.0 to 100, and preferably are from 1.8 to10.

Since the product of the present process is a random distribution ofpolymer segments, the product may comprise a portion of unattachedpolymer segments. The fraction of unattached segments may becharacterized by any suitable analytical technique, such as TREF orATREF. In general, the quantity of unattached segments ranges from 2 to98 percent, preferably from 2 to 5 percent. The fraction of unattachedsequences may be varied depending on the nature of the unsaturatedpolymer reagents and the intended end use of the resulting polymerproduct.

Metathesis Products

The copolymer products of the invention comprise a random distributionof polymer blocks and block lengths. The length distribution of theblocks is dependent on the length distribution of the segments in theinitial polymer reagents and the extent of metathesis conducted. Thepolymers of the invention are distinguished from pure diblock, triblock,or other copolymers due to the presence of random polymer blockconnectivity and a statistical distribution of block lengths. If morethan two polymer types are present and/or pendant chain unsaturationsare present initially or generated during the metathesis process,additional polymer types, such as comb polymers will be present in theresulting product.

Linear polymers result when linear unsaturated polymers having one ormore backbone unsaturations are metathesized. Branching in polymerproducts results when unsaturated polymers having a combination ofbackbone unsaturation and pendant unsaturation, including unsaturatedlong-chain branches, are metathesized. Comb polymers are formed when oneor more unsaturated parent polymers has predominantly pendantunsaturation and at least one other unsaturated parent polymer haspredominantly backbone unsaturation. For the special case where oneunsaturated parent polymer contains predominantly pendant vinylfunctionality, a crosslinked network may result, giving polymersincluding lightly cross-linked or fully vulcanized products. Terminal,unsaturation, on the other hand, has no net effect on the presentprocess and simply generates a relatively long terminal block in theresulting product. Preferably most or substantially all of the ethylenicunsaturation in the reagent polymers is non-terminating unsaturation.

Specific non-limiting polymer products obtainable according to thepresent invention include those resulting from metathesis of thefollowing combination or unsaturated reagent polymers. In all cases thevalue Tm or Tg may be actual or expected.

A. Unsaturated Branched Polyethylene+Unsaturated Diene Rubber

1. The cross-metathesized product preferably is comprised of segments ofamorphous polyethylene (soft segments) having an associated T_(g1) andsegments of an elastomeric diene polymer (soft segments) having aassociated T_(g2) or short chain non-polymeric segments, especially ifhighly unsaturated diene polymers are used (unsaturation levels in thediene polymer of 10-50, preferably 10-48, mole percent). Use of polargroup containing diene elastomers, especially 2-chloro-1,3-butadiene,2-fluoro-1,3-butadiene, or acrylonitrile/1,3-butadiene copolymers, giveselastomer products having improved compatibility with polyolefins suchas polyethylene.

2. The mass fraction of branched polyethylene segments in the polymerproduct, desirably varies from 4 to 96 percent. The mass fraction ofunattached low density polyethylene desirably is less than 50 percent,preferably less than or equal to 25 percent.

In the Foregoing Embodiments:

T_(g1) preferably is greater than T_(g2), more preferably at least 25°C. greater than T_(g2), and most preferably at least 50° C. greater thanT_(g2).

B. Unsaturated Polypropylene/Ethylene Copolymer+Unsaturated Diene Rubber

1. The cross-metathesized product preferably is comprised ofpropylene/ethylene copolymer segments having an associated T_(g1) andsegments of an elastomeric diene polymer having an associated T_(g2) orshort chain non-polymeric segments, especially if highly unsaturateddiene polymers are used (unsaturation levels in the diene polymer of10-50, preferably 10-48, mole percent). Use of polar group containingdiene elastomers, especially 2-chloro-1,3-butadiene,2-fluoro-1,3-butadiene, or acrylonitrile/1,3-butadiene copolymers, giveselastomer products having improved compatibility with polyolefins suchas polypropylene.

2. The polymer can optionally contain crystalline or semi-crystallinepolypropylene segments with associated crystalline melting point or Tm.

3. The mass fraction of propylene/ethylene elastomer segments desirablyis from 4 to 96 percent. Further desirably, the mass fraction ofunattached polypropylene is less than 50 percent, preferably less thanor equal to 25 percent.

In the Foregoing Embodiments:

Tm is greater than 100° C., more preferably greater than 130° C., andmost preferably greater than 150° C.;

T_(g1) preferably is greater than T_(g2), more preferably at least 25°C. greater than T_(g2), and most preferably at least 50° C. greater thanT_(g2).

C. Unsaturated Polar Group Containing Amorphous Polymer+UnsaturatedDiene Rubber

1. The cross-metathesized product preferably is comprised of segments ofpolar group containing amorphous polymer having an associated T_(g1) andsegments of an elastomeric diene polymer having an associated T_(g2) orshort chain non-polymeric segments, especially if highly unsaturateddiene polymers are used (unsaturation of 10-50, preferably 10-48, molepercent).

2. The mass fraction of polar group containing amorphous polymer in theproduct desirably varies from 4 to 96 percent. The mass fraction ofunattached polar group containing polymer desirably is less than 50percent, preferably less than or equal to 25 percent.

In the Foregoing Embodiments:

T_(g1) preferably is greater than T_(g2), more preferably at least 25°C. greater than T_(g2), and most preferably at least 50° C. greater thanT_(g2).

D. Unsaturated Polar Group Containing Amorphous Polymer+UnsaturatedPolar Group Containing Diene Elastomer

1. The cross-metathesized product preferably is comprised of segments ofpolar group containing amorphous polymer having an associated T_(g1) andsegments of an elastomeric polar group containing diene polymer (softsegments) having an associated T_(g2) or short chain non-polymericsegments, especially if highly unsaturated diene polymers are used(unsaturation of 10-50, preferably 10-48, mole percent). Use ofpoly(2-chloro-1,3-butadiene), poly(2-fluoro-1,3-butadiene), oracrylonitrile/1,3-butadiene copolymers, are preferred for forming polargroup substituted diene polymers.

2. The mass fraction of polar group containing amorphous polymersegments in the copolymer product desirably varies from 4 to 96 percent.The mass fraction of unattached polar group containing amorphous polymersegments desirably is less than 50 percent, preferably less than orequal to 25 percent.

In the Foregoing Embodiments:

T_(g1) preferably is greater than T_(g2), more preferably at least 25°C. greater than T_(g2), and most preferably at least 50° C. greater thanT_(g2).

Identification of the various polymer segments is conducted by use ofCRYSTAF, TREF, ATREF, DSC, IR or NMR techniques, or combinationsthereof.

Unsaturated Reagent Polymer Synthesis by Addition Polymerization

A preferred process for preparing unsaturated hard segment reagentpolymers for use herein is the addition polymerization of ethylene, oneor more α-olefins and a diolefin. Suitable catalysts for suchcopolymerization include the well known transition metal basedcoordination catalysts previously disclosed for use in polymerizationsof olefin monomers. Especially preferred catalysts comprise a Group 4metal, especially zirconium or hafnium, and a heteroatom containingdonor ligand. Desirable catalysts produce interpolymer products that arelow in terminal unsaturation. The presence of unsaturation in thepolymer, especially terminal unsaturation, may be further reduced byhydrogenation of the resulting interpolymer prior to contact with themetathesis catalyst. Desirably, the incidence of olefinic unsaturationin the unsaturated polymer is adjusted to between 0.01 and 0.1 percent,with the terminal unsaturation being not more than 0.001 percent,preferably less than 0.0001 percent. In determining such values, theethylene units and any substituents on either carbon thereof areincluded in the theoretical weights of the ethylenic unit.

Examples of suitable Group 4 metal complexes useful as coordinationcatalyst components include complexes of transition metals selected fromGroups 3 to 15 of the Periodic Table of the Elements containing one ormore delocalized, π-bonded ligands or polyvalent Lewis base ligands.Examples include metallocene, half-metallocene, constrained geometry,and polyvalent pyridylamine-, polyether-, or other polychelating basecomplexes. The complexes are generically depicted by the formula:MK_(k)X_(x)Z_(z), or a dimer thereof, wherein

M is a metal selected from Groups 3-15, preferably 3-10, more preferably4-8, and most preferably Group 4 of the Periodic Table of the Elements;

K independently each occurrence is a group containing delocalizedπ-electrons or one or more electron pairs through which K is bound to M,said K group containing up to 50 atoms not counting hydrogen atoms,optionally two or more K groups may be joined together forming a bridgedstructure, and further optionally one or more K groups may be bound toZ, to X or to both Z and X;

X independently each occurrence is a monovalent, anionic moiety havingup to 40 non-hydrogen atoms, optionally one or more X groups may bebonded together thereby forming a divalent or polyvalent anionic group,and, further optionally, one or more X groups and one or more Z groupsmay be bonded together thereby forming a moiety that is both covalentlybound to M and coordinated thereto;

Z independently each occurrence is a neutral, Lewis base donor ligand ofup to 50 non-hydrogen atoms containing at least one unshared electronpair through which Z is coordinated to M;

k is an integer from 0 to 3;

x is an integer from 1 to 4;

z is a number from 0 to 3; and

the sum, k+x, is equal to the formal oxidation state of M.

Suitable metal complexes include those containing from 1 to 3 π-bondedanionic or neutral ligand groups, which may be cyclic or non-cyclicdelocalized π-bonded anionic ligand groups. Exemplary of such π-bondedgroups are conjugated or nonconjugated, cyclic or non-cyclic diene anddienyl groups, allyl groups, boratabenzene groups, phosphole, and arenegroups. By the term “π-bonded” is meant that the ligand group is bondedto the transition metal by a sharing of electrons from a partiallydelocalized π-bond.

Each atom in the delocalized π-bonded group may independently besubstituted with a radical selected from the group consisting ofhydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substitutedheteroatoms wherein the heteroatom is selected from Group 14-16 of thePeriodic Table of the Elements, and such hydrocarbyl-substitutedheteroatom radicals further substituted with a Group 15 or 16 heteroatom containing moiety. In addition two or more such radicals maytogether form a fused ring system, including partially or fullyhydrogenated fused ring systems, or they may form a metallocycle withthe metal. Included within the term “hydrocarbyl” are C₁₋₂₀ straight,branched and cyclic alkyl radicals, C₆₋₂₀ aromatic radicals, C₇₋₂₀alkyl-substituted aromatic radicals, and C₇₋₂₀ aryl-substituted alkylradicals. Suitable hydrocarbyl-substituted heteroatom radicals includemono-, di- and tri-substituted radicals of boron, silicon, germanium,nitrogen, phosphorus or oxygen wherein each of the hydrocarbyl groupscontains from 1 to 20 carbon atoms. Examples include N,N-dimethylamino,pyrrolidinyl, trimethylsilyl, trimethylsilyl, t-butyldimethylsilyl,methyldi(t-butyl)silyl, triphenylgermyl, and trimethylgermyl groups.Examples of Group 15 or 16 hetero atom containing moieties includeamino, phosphino, alkoxy, or alkylthio moieties or divalent derivativesthereof, for example, amide, phosphide, alkyleneoxy or alkylenethiogroups bonded to the transition metal or Lanthanide metal, and bonded tothe hydrocarbyl group, π-bonded group, or hydrocarbyl-substitutedheteroatom.

Examples of suitable anionic, delocalized π-bonded groups includecyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl,dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups,phosphole, and boratabenzyl groups, as well as inertly substitutedderivatives thereof, especially C₁₋₁₀ hydrocarbyl-substituted ortris(C₁₋₁₀ hydrocarbyl)silyl-substituted derivatives thereof. Preferredanionic delocalized π-bonded groups are cyclopentadienyl,pentamethylcyclopentadienyl, tetramethylcyclopentadienyl,tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl,fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl,tetrahydrofluorenyl, octahydrofluorenyl, 1-indacenyl,3-pyrrolidinoinden-1-yl, 3,4-(cyclopenta(l)phenanthren-1-yl, andtetrahydroindenyl.

The boratabenzenyl ligands are anionic ligands which are boroncontaining analogues to benzene. They are previously known in the arthaving been described by G. Herberich, et al., in Organometallics, 14,1,471-480 (1995). Preferred boratabenzenyl ligands correspond to theformula:

wherein R¹ is an inert substituent, preferably selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, halo or germyl, said R¹having up to 20 atoms not counting hydrogen, and optionally two adjacentR¹ groups may be joined together. In complexes involving divalentderivatives of such delocalized π-bonded groups one atom thereof isbonded by means of a covalent bond or a covalently bonded divalent groupto another atom of the complex thereby forming a bridged system.

Phospholes are anionic ligands that are phosphorus containing analoguesto a cyclopentadienyl group. They are previously known in the art havingbeen described by WO 98/50392, and elsewhere. Preferred phospholeligands correspond to the formula:

wherein R¹ is as previously defined.

Preferred transition metal complexes for use herein correspond to theformula: MK_(k)X_(x)Z_(z), or a dimer thereof, wherein:

M is a Group 4 metal;

K is a group containing delocalized π-electrons through which K is boundto M, said K group containing up to 50 atoms not counting hydrogenatoms, optionally two K groups may be joined together forming a bridgedstructure, and further optionally one K may be bound to X or Z;

X each occurrence is a monovalent, anionic moiety having up to 40non-hydrogen atoms, optionally one or more X and one or more K groupsare bonded together to form a metallocycle, and further optionally oneor more X and one or more Z groups are bonded together thereby forming amoiety that is both covalently bound to M and coordinated thereto;

Z independently each occurrence is a neutral, Lewis base donor ligand ofup to 50 non-hydrogen atoms containing at least one unshared electronpair through which Z is coordinated to M;

k is an integer from 0 to 3;

x is an integer from 1 to 4;

z is a number from 0 to 3; and

the sum, k+x, is equal to the formal oxidation state of M.

Preferred complexes include those containing either one or two K groups.The latter complexes include those containing a bridging group linkingthe two K groups. Preferred bridging groups are those corresponding tothe formula (ER′₂)_(e) wherein E is silicon, germanium, tin, or carbon,R′ independently each occurrence is hydrogen or a group selected fromsilyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R′having up to 30 carbon or silicon atoms, and e is 1 to 8. Preferably, R′independently each occurrence is methyl, ethyl, propyl, benzyl,tert-butyl, phenyl, methoxy, ethoxy or phenoxy.

Examples of the complexes containing two K groups are compoundscorresponding to the formula:

wherein:

M is titanium, zirconium or hafnium, preferably zirconium or hafnium, inthe +2 or +4 formal oxidation state;

R³ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R³ having up to 20 non-hydrogen atoms, oradjacent R³ groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system, and

X″ independently each occurrence is an anionic ligand group of up to 40non-hydrogen atoms, or two X″ groups together form a divalent anionicligand group of up to 40 non-hydrogen atoms or together are a conjugateddiene having from 4 to 30 non-hydrogen atoms bound by means ofdelocalized π-electrons to M, whereupon M is in the +2 formal oxidationstate, and

R′, E and e are as previously defined.

Exemplary bridged ligands containing two π-bonded groups are:dimethylbis(cyclopentadienyl)silane,dimethylbis(tetramethylcyclopentadienyl)silane,dimethylbis(2-ethylcyclopentadien-1-yl)silane,dimethylbis(2-t-butylcyclopentadien-1-yl)silane,2,2-bis(tetramethylcyclopentadienyl)propane,dimethylbis(inden-1-yl)silane, dimethylbis(tetrahydroinden-1-yl)silane,dimethylbis(fluoren-1-yl)silane,dimethylbis(tetrahydrofluoren-1-yl)silane,dimethylbis(2-methyl-4-phenylinden-1-yl)-silane,dimethylbis(2-methylinden-1-yl)silane,dimethyl(cyclopentadienyl)(fluoren-1-yl)silane,dimethyl(cyclopentadienyl)(octahydrofluoren-1-yl)silane,dimethyl(cyclopentadienyl)(tetrahydrofluoren-1-yl)silane,(1,1,2,2-tetramethy)-1,2-bis(cyclopentadienyl)disilane,(1,2-bis(cyclopentadienyl)ethane, anddimethyl(cyclopentadienyl)-1-(fluoren-1-yl)methane.

Preferred X″ groups are selected from hydride, hydrocarbyl, silyl,germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl andaminohydrocarbyl groups, or two X″ groups together form a divalentderivative of a conjugated diene or else together they form a neutral,π-bonded, conjugated diene. Most preferred X″ groups are C₁₋₂₀hydrocarbyl groups.

Examples of metal complexes of the foregoing formula suitable for use inthe present invention include:

bis(cyclopentadienyl)zirconiumdimethyl, bis(cyclopentadienyl)zirconiumdibenzyl, bis(cyclopentadienyl)zirconium methyl benzyl,bis(cyclopentadienyl)zirconium methyl phenyl,bis(cyclopentadienyl)zirconiumdiphenyl,bis(cyclopentadienyl)titanium-allyl,bis(cyclopentadienyl)zirconiummethylmethoxide,bis(cyclopentadienyl)zirconiummethylchloride,bis(pentamethylcyclopentadienyl)zirconiumdimethyl,bis(pentamethylcyclopentadienyl)titaniumdimethyl,bis(indenyl)zirconiumdimethyl, indenylfluorenylzirconiumdimethyl,bis(indenyl)zirconiummethyl(2-(dimethylamino)benzyl),bis(indenyl)zirconiummethyltrimethylsilyl,bis(tetrahydroindenyl)zirconiummethyltrimethylsilyl,bis(pentamethylcyclopentadienyl)zirconiummethylbenzyl,bis(pentamethylcyclopentadienyl)zirconiumdibenzyl,bis(pentamethylcyclopentadienyl)zirconiummethylmethoxide,bis(pentamethylcyclopentadienyl)zirconiummethylchloride,bis(methylethylcyclopentadienyl)zirconiumdimethyl,bis(butylcyclopentadienyl)zirconiumdibenzyl,bis(t-butylcyclopentadienyl)zirconiumdimethyl,bis(ethyltetramethylcyclopentadienyl)zirconiumdimethyl,bis(methylpropylcyclopentadienyl)zirconiumdibenzyl,bis(trimethylsilylcyclopentadienyl)zirconiumdibenzyl,dimethylsilylbis(cyclopentadienyl)zirconiumdichloride,dimethylsilylbis(cyclopentadienyl)zirconiumdimethyl,dimethylsilylbis(tetramethylcyclopentadienyl)titanium(III) allyldimethylsilylbis(t-butylcyclopentadienyl)zirconiumdichloride,dimethylsilylbis(n-butylcyclopentadienyl)zirconiumdichloride,(dimethylsilylbis(tetramethylcyclopentadienyl)titanium(III)2-(dimethylamino)benzyl,(dimethylsilylbis(n-butylcyclopentadienyl)titanium(III)2-(dimethylamino)benzyl, dimethylsilylbis(indenyl)zirconiumdichloride,dimethylsilylbis(indenyl)zirconiumdimethyl,dimethylsilylbis(2-methylindenyl)zirconiumdimethyl,dimethylsilylbis(2-methyl-4-phenylindenyl)zirconiumdimethyl,dimethylsilylbis(2-methylindenyl)zirconium-1,4-diphenyl-1,3-butadiene,dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium(II)1,4-diphenyl-1,3-butadiene,dimethylsilylbis(4,5,6,7-tetrahydroinden-1-yl)zirconiumdichloride,dimethylsilylbis(4,5,6,7-tetrahydroinden-1-yl)zirconiumdimethyl,dimethylsilylbis(tetrahydroindenyl)zirconium(II)1,4-diphenyl-1,3-butadiene,dimethylsilylbis(tetramethylcyclopentadienyl)zirconium dimethyldimethylsilylbis(fluorenyl)zirconiumdimethyl,dimethylsilylbis(tetrahydrofluorenyl)zirconium bis(trimethylsilyl),ethylenebis(indenyl)zirconiumdichloride,ethylenebis(indenyl)zirconiumdimethyl,ethylenebis(4,5,6,7-tetrahydroindenyl)zirconiumdichloride,ethylenebis(4,5,6,7-tetrahydroindenyl)zirconiumdimethyl,(isopropylidene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzyl, anddimethylsilyl(tetramethylcyclopentadienyl)(fluorenyl)zirconium dimethyl.

A further class of metal complexes utilized in the present inventioncorresponds to the preceding formula: MKZ_(z)X_(x), or a dimer thereof,wherein M, K, X, x and z are as previously defined, and Z is asubstituent of up to 50 non-hydrogen atoms that together with K forms ametallocycle with M.

Preferred Z substituents include groups containing up to 30 non-hydrogenatoms comprising at least one atom that is oxygen, sulfur, boron or amember of Group 14 of the Periodic Table of the Elements directlyattached to K, and a different atom, selected from the group consistingof nitrogen, phosphorus, oxygen or sulfur that is covalently bonded toM.

More specifically this class of Group 4 metal complexes used accordingto the present invention includes “constrained geometry catalysts”corresponding to the formula:

wherein:

M is titanium or zirconium, preferably titanium in the +2, +3, or +4formal oxidation state;

K¹ is a delocalized, π-bonded ligand group optionally substituted withfrom 1 to 5 R² groups,

R² in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R² having up to 20 non-hydrogen atoms, oradjacent R² groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system,

each X is a halo, hydrocarbyl, hydrocarbyloxy or silyl group, said grouphaving up to 20 non-hydrogen atoms, or two X groups together form aneutral C₅₋₃₀ conjugated diene or a divalent derivative thereof;

x is 1 or 2;

Y is —O—, —S—, —NR′—, —PR′—; and

X′ is SiR′₂, CR′₂, SiR′₂SiR′₂, CR′₂CR′₂, CR′═CR′, CR′₂SiR′₂, or GeR′₂,wherein

R′ independently each occurrence is hydrogen or a group selected fromsilyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R′having up to 30 carbon or silicon atoms.

Specific examples of the foregoing constrained geometry metal complexesinclude compounds corresponding to the formula:

wherein,

Ar is an aryl group of from 6 to 30 atoms not counting hydrogen;

R⁴ independently each occurrence is hydrogen, Ar, or a group other thanAr selected from hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl,halide, hydrocarbyloxy, trihydrocarbylsiloxy,bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino,hydrocarbadiylamino, hydrocarbylimino, di(hydrocarbyl)phosphino,hydrocarbadiylphosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R group having up to 40atoms not counting hydrogen atoms, and optionally two adjacent R⁴ groupsmay be joined together forming a polycyclic fused ring group;

M is titanium;

X′ is SiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶ ₂SiR⁶ ₂,BR⁶, BR⁶L″, or GeR⁶ ₂;

Y is —O—, —S—, —NR⁵—, —PR⁵—; —NR⁵ ₂, or —PR⁵ ₂;

R⁵, independently each occurrence, is hydrocarbyl, trihydrocarbylsilyl,or trihydrocarbylsilylhydrocarbyl, said R⁵ having up to 20 atoms otherthan hydrogen, and optionally two R⁵ groups or R⁵ together with Y or Zform a ring system;

R⁶, independently each occurrence, is hydrogen, or a member selectedfrom hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenatedaryl, —NR⁵ ₂, and combinations thereof, said R⁶ having up to 20non-hydrogen atoms, and optionally, two R⁶ groups or R⁶ together with Zforms a ring system;

Z is a neutral diene or a monodentate or polydentate Lewis baseoptionally bonded to R⁵, R⁶, or X;

X is hydrogen, a monovalent anionic ligand group having up to 60 atomsnot counting hydrogen, or two X groups are joined together therebyforming a divalent ligand group;

x is 1 or 2; and

z is 0, 1 or 2.

Preferred examples of the foregoing metal complexes are substituted atboth the 3- and 4-positions of a cyclopentadienyl or indenyl group withan Ar group.

Examples of the foregoing metal complexes include:

-   (3-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II)    1,3-diphenyl-1,3-butadiene;-   (3-(pyrrol-1-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-(pyrrol-1-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-(pyrrol-1-yl)cyclopentadien-1-yl))dimethyl(t-butylamido)silanetitanium(II)    1,4-diphenyl-1,3-butadiene;-   (3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II)    1,4-diphenyl-1,3-butadiene;-   (3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II)    1,3-pentadiene;-   (3-(3-N,N-dimethylamino)phenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-(3-N,N-dimethylamino)phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-(3-N,N-dimethylamino)phenyl    cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-(4-methoxyphenyl)-4-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-(4-methoxyphenyl)-4-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-4-methoxyphenyl)-4-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II)    1,4-diphenyl-1,3-butadiene;-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II)    1,4-diphenyl-1,3-butadiene;-   (3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   ((2,3-diphenyl)-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silane    titanium dichloride,-   ((2,3-diphenyl)-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silane    titanium dimethyl,-   ((2,3-diphenyl)-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II)    1,4-diphenyl-1,3-butadiene;-   (2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II)    1,4-diphenyl-1,3-butadiene;-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II)    1,4-diphenyl-1,3-butadiene;-   (2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II)    1,4-diphenyl-1,3-butadiene;-   (2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl, and-   (2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II)    1,4-diphenyl-1,3-butadiene.

Additional examples of suitable metal complexes for use as additionpolymerization catalysts are polycyclic complexes corresponding to theformula:

where M is titanium in the +2, +3 or +4 formal oxidation state;

R⁷ independently each occurrence is hydride, hydrocarbyl, silyl, germyl,halide, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino,di(hydrocarbyl)amino, hydrocarbyleneamino, di(hydrocarbyl)phosphino,hydrocarbylene-phosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl-substitutedhydrocarbyl, hydrocarbylsiloxy-substituted hydrocarbyl,hydrocarbylsilylamino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylene-phosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R⁷ group having up to40 atoms not counting hydrogen, and optionally two or more of theforegoing groups may together form a divalent derivative;

R⁸ is a divalent hydrocarbylene- or substituted hydrocarbylene groupforming a fused system with the remainder of the metal complex, said R⁸containing from 1 to 30 atoms not counting hydrogen;

X^(a) is a divalent moiety, or a moiety comprising one σ-bond and aneutral two electron pair able to form a coordinate-covalent bond to M,said X^(a) comprising boron, or a member of Group 14 of the PeriodicTable of the Elements, and also comprising nitrogen, phosphorus, sulfuror oxygen;

X is a monovalent anionic ligand group having up to 60 atoms exclusiveof the class of ligands that are cyclic, delocalized, π-bound ligandgroups and optionally two X groups together form a divalent ligandgroup;

Z independently each occurrence is a neutral ligating compound having upto 20 atoms;

x is 0, 1 or 2; and

z is zero or 1.

Preferred examples of such complexes are 3-phenyl-substituteds-indecenyl complexes corresponding to the formula:

2,3-dimethyl-substituted s-indecenyl complexes corresponding to theformulas:

or 2-methyl-substituted s-indecenyl complexes corresponding to theformulas:

Additional examples of such metal complexes include those of theformula:

Specific metal complexes include:

-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(II) 1,4-diphenyl-1,3-butadiene,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(II) 1,3-pentadiene,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(III) 2-(N,N-dimethylamino)benzyl,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(IV) dichloride,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(IV) dimethyl,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(IV) dibenzyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(II) 1,4-diphenyl-1,3-butadiene,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(II) 1,3-pentadiene,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(III) 2-(N,N-dimethylamino)benzyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(IV) dichloride,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(IV) dimethyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(IV) dibenzyl,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(II) 1,4-diphenyl-1,3-butadiene,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(II) 1,3-pentadiene,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(III) 2-(N,N-dimethylamino)benzyl,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(IV) dichloride,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(IV) dimethyl,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(IV) dibenzyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(II) 1,4-diphenyl-1,3-butadiene,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(II) 1,3-pentadiene,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(III) 2-(N,N-dimethylamino)benzyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(IV) dichloride,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(IV) dimethyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium(IV) dibenzyl, and mixtures thereof, especially mixtures of    positional isomers.

Further illustrative examples of metal complexes for use in additionpolymerization processes correspond to the formula:

where M is titanium in the +2, +3 or +4 formal oxidation state;

T is —NR⁹— or —O—;

R⁹ is hydrocarbyl, silyl, germyl, dihydrocarbylboryl, or halohydrocarbylor up to 10 atoms not counting hydrogen;

R¹⁰ independently each occurrence is hydrogen, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, germyl, halide,hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino,di(hydrocarbyl)amino, hydrocarbyleneamino, di(hydrocarbyl)phosphino,hydrocarbylene-phosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl-substitutedhydrocarbyl, hydrocarbylsiloxy-substituted hydrocarbyl,hydrocarbylsilylamino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R¹⁰ group having up to40 atoms not counting hydrogen atoms, and optionally two or more of theforegoing adjacent R¹⁰ groups may together form a divalent derivativethereby forming a saturated or unsaturated fused ring;

X^(a) is a divalent moiety lacking in delocalized π-electrons, or such amoiety comprising one σ-bond and a neutral two electron pair able toform a coordinate-covalent bond to M, said X′ comprising boron, or amember of Group 14 of the Periodic Table of the Elements, and alsocomprising nitrogen, phosphorus, sulfur or oxygen;

X is a monovalent anionic ligand group having up to 60 atoms exclusiveof the class of ligands that are cyclic ligand groups bound to M throughdelocalized π-electrons or two X groups together are a divalent anionicligand group;

Z independently each occurrence is a neutral ligating compound having upto 20 atoms;

x is 0, 1, 2, or 3; and

z is 0 or 1.

Highly preferably T is ═N(CH₃), X is halo or hydrocarbyl, x is 2, X′ isdimethylsilane, z is 0, and R¹⁰ each occurrence is hydrogen, ahydrocarbyl, hydrocarbyloxy, dihydrocarbylamino, hydrocarbyleneamino,dihydrocarbylamino-substituted hydrocarbyl group, orhydrocarbyleneamino-substituted hydrocarbyl group of up to 20 atoms notcounting hydrogen, and optionally two R¹⁰ groups may be joined together.

Illustrative metal complexes of the foregoing formulas include thefollowing compounds:

-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (II)    1,4-diphenyl-1,3-butadiene,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (II)    1,3-pentadiene,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (III)    2-(N,N-dimethylamino)benzyl,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dichloride,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dimethyl,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dibenzyl,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    bis(trimethylsilyl),-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(II)    1,4-diphenyl-1,3-butadiene,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(II)    1,3-pentadiene,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(III)    2-(N,N-dimethylamino)benzyl,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV)    dichloride,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV)    dimethyl,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV)    dibenzyl,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV)    bis(trimethylsilyl),-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(II)    1,4-diphenyl-1,3-butadiene,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(II)    1,3-pentadiene,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(III)    2-(N,N-dimethylamino)benzyl,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV)    dichloride,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV)    dimethyl,-   (t-butylamido)di(p-methylphenyl)-[6,7]-benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV)    dibenzyl,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV)    bis(trimethylsilyl),-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(II)    1,4-diphenyl-1,3-butadiene,-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(II)    1,3-pentadiene,-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(III)    2-(N,N-dimethylamino)benzyl,-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV)    dichloride,-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV)    dimethyl,-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV)    dibenzyl; and-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV)    bis(trimethylsilyl).

Illustrative Group 4 metal complexes that may be employed in thepractice of the present invention further include:

-   (tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,-   (tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)    dimethylsilanetitanium dibenzyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium    dimethyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitanium    dimethyl,-   (tert-butylamido)(tetramethyl-η⁵-indenyl)dimethylsilanetitanium    dimethyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilane    titanium(III) 2-(dimethylamino)benzyl;-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(III)    allyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(III)    2,4-dimethylpentadienyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II)    1,4-diphenyl-1,3-butadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II)    1,3-pentadiene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(II)    1,4-diphenyl-1,3-butadiene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(II)    2,4-hexadiene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV)    2,3-dimethyl-1,3-butadiene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV)    isoprene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV)    1,3-butadiene,-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV)    2,3-dimethyl-1,3-butadiene,-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)    isoprene-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)    dimethyl-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV)    dibenzyl-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)    1,3-butadiene,-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II)    1,3-pentadiene,-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(II)    1,4-diphenyl-1,3-butadiene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(II)    1,3-pentadiene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV)    dimethyl,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV)    dibenzyl,-   (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II)    1,4-diphenyl-1,3-butadiene,-   (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II)    1,3-pentadiene,-   (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II)    2,4-hexadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium(IV)    1,3-butadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(IV)    2,3-dimethyl-1,3-butadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(IV)    isoprene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium(II)    1,4-dibenzyl-1,3-butadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II)    2,4-hexadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium(II)    3-methyl-1,3-pentadiene,-   (tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethylsilanetitaniumdimethyl,-   (tert-butylamido)(6,6-dimethylcyclohexadienyl)dimethylsilanetitaniumdimethyl,    (tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl,-   (tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl-   (tert-butylamido)(tetramethyl-η₅-cyclopentadienyl    methylphenylsilanetitanium(IV) dimethyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl    methylphenylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene,-   1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyltitanium(IV)    dimethyl, and-   1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyl-titanium(II)    1,4-diphenyl-1,3-butadiene.

Other delocalized, π-bonded complexes, especially those containing otherGroup 4 metals, will, of course, be apparent to those skilled in theart, and are disclosed among other places in: WO 03/78480, WO 03/78483,WO 02/92610, WO 02/02577, US 2003/0004286 and U.S. Pat. Nos. 6,515,155,6,555,634, 6,150,297, 6,034,022, 6,268,444, 6,015,868, 5,866,704, and5,470,993.

Additional examples of metal complexes that are usefully employed aremetal complexes of polyvalent Lewis bases, such as compounds of theformulas:

wherein T^(b) is a bridging group, preferably containing 2 or more atomsother than hydrogen,

X^(b) and Y^(b) are each independently selected from the groupconsisting of nitrogen, sulfur, oxygen and phosphorus; more preferablyboth X^(b) and Y^(b) are nitrogen,

R^(b) and R^(b)′ independently each occurrence are hydrogen or C₁₋₅₀hydrocarbyl groups optionally containing one or more heteroatoms orinertly substituted derivative thereof. Non-limiting examples ofsuitable R^(b) and R^(b)′ groups include alkyl, alkenyl, aryl, aralkyl,(poly)alkylaryl and cycloalkyl groups, as well as nitrogen, phosphorus,oxygen and halogen substituted derivatives thereof. Specific examples ofsuitable Rb and Rb′ groups include methyl, ethyl, isopropyl, octyl,phenyl, 2,6-dimethylphenyl, 2,6-di(isopropyl)phenyl,2,4,6-trimethylphenyl, pentafluorophenyl, 3,5-trifluoromethylphenyl, andbenzyl;

g is 0 or 1;

M^(b) is a metallic element selected from Groups 3 to 15, or theLanthanide series of the Periodic Table of the Elements. Preferably,M^(b) is a Group 3-13 metal, more preferably M^(b) is a Group 4-10metal;

L^(b) is a monovalent, divalent, or trivalent anionic ligand containingfrom 1 to 50 atoms, not counting hydrogen. Examples of suitable L^(b)groups include halide; hydride; hydrocarbyl, hydrocarbyloxy;di(hydrocarbyl)amido, hydrocarbyleneamido, di(hydrocarbyl)phosphido;hydrocarbylsulfido; hydrocarbyloxy, tri(hydrocarbylsilyl)alkyl; andcarboxylates. More preferred L^(b) groups are C₁₋₂₀ alkyl, C₇₋₂₀aralkyl, and chloride;

h is an integer from 1 to 6, preferably from 1 to 4, more preferablyfrom 1 to 3, and j is 1 or 2, with the value h×j selected to providecharge balance;

Z^(b) is a neutral ligand group coordinated to M^(b), and containing upto 50 atoms not counting hydrogen Preferred Z^(b) groups includealiphatic and aromatic amines, phosphines, and ethers, alkenes,alkadienes, and inertly substituted derivatives thereof. Suitable inertsubstituents include halogen, alkoxy, aryloxy, alkoxycarbonyl,aryloxycarbonyl, di(hydrocarbyl)amine, tri(hydrocarbyl)silyl, andnitrile groups. Preferred Z^(b) groups include triphenylphosphine,tetrahydrofuran, pyridine, and 1,4-diphenylbutadiene;

f is an integer from 1 to 3;

two or three of T^(b), R^(b) and R^(b)′ may be joined together to form asingle or multiple ring structure;

h is an integer from 1 to 6, preferably from 1 to 4, more preferablyfrom 1 to 3;

indicates any form of electronic interaction, especially coordinate orcovalent bonds, including multiple bonds, arrows signify coordinatebonds, and dotted lines indicate optional double bonds.

In one embodiment, it is preferred that R^(b) have relatively low sterichindrance with respect to X^(b). In this embodiment, most preferredR^(b) groups are straight chain alkyl groups, straight chain alkenylgroups, branched chain alkyl groups wherein the closest branching pointis at least 3 atoms removed from X^(b), and halo, dihydrocarbylamino,alkoxy or trihydrocarbylsilyl substituted derivatives thereof. Highlypreferred R^(b) groups in this embodiment are C₁₋₈ straight chain alkylgroups.

At the same time, in this embodiment R^(b)′ preferably has relativelyhigh steric hindrance with respect to Y^(b). Non-limiting examples ofsuitable R^(b)′ groups for this embodiment include alkyl or alkenylgroups containing one or more secondary or tertiary carbon centers,cycloalkyl, aryl, alkaryl, aliphatic or aromatic heterocyclic groups,organic or inorganic oligomeric, polymeric or cyclic groups, and halo,dihydrocarbylamino, alkoxy or trihydrocarbylsilyl substitutedderivatives thereof. Preferred R^(b)′ groups in this embodiment containfrom 3 to 40, more preferably from 3 to 30, and most preferably from 4to 20 atoms not counting hydrogen and are branched or cyclic.

Examples of preferred T^(b) groups are structures corresponding to thefollowing formulas:

wherein

Each R^(d) is C₁₋₁₀ hydrocarbyl group, preferably methyl, ethyl,n-propyl, i-propyl, t-butyl, phenyl, 2,6-dimethylphenyl, benzyl, ortolyl. Each R^(e) is C₁₋₁₀ hydrocarbyl, preferably methyl, ethyl,n-propyl, i-propyl, t-butyl, phenyl, 2,6-dimethylphenyl, benzyl, ortolyl. In addition, two or more R^(d) or R^(e) groups, or mixtures of Rdand Re groups may together form a polyvalent derivative of a hydrocarbylgroup, such as, 1,4-butylene, 1,5-pentylene, or a multicyclic, fusedring, polyvalent hydrocarbyl- or heterohydrocarbyl-group, such asnaphthalene-1,8-diyl.

Preferred examples of the foregoing polyvalent Lewis base complexesinclude:

wherein R^(d′) each occurrence is independently selected from the groupconsisting of hydrogen and C₁₋₅₀ hydrocarbyl groups optionallycontaining one or more heteroatoms, or inertly substituted derivativethereof, or further optionally, two adjacent R^(d′) groups may togetherform a divalent bridging group;

d′ is 4;

M^(b′) is a Group 4 metal, preferably titanium or hafnium, or a Group 10metal, preferably Ni or Pd;

L^(b′) is a monovalent ligand of up to 50 atoms not counting hydrogen,preferably halide or hydrocarbyl, or two L^(b′) groups together are adivalent or neutral ligand group, preferably a C₂₋₅₀ hydrocarbylene,hydrocarbadiyl or diene group.

The polyvalent Lewis base complexes additionally include Group 4 metalderivatives, especially hafnium derivatives of hydrocarbylaminesubstituted heteroaryl compounds corresponding to the formula:

wherein:

R¹¹ is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl,aryl, and inertly substituted derivatives thereof containing from 1 to30 atoms not counting hydrogen or a divalent derivative thereof;

T¹ is a divalent bridging group of from 1 to 41 atoms other thanhydrogen, preferably 1 to 20 atoms other than hydrogen, and mostpreferably a mono- or di-C₁₋₂₀ hydrocarbyl substituted methylene orsilane group; and

R¹² is a C₅₋₂₀ heteroaryl group containing Lewis base functionality,especially a pyridin-2-yl- or substituted pyridin-2-yl group or adivalent derivative thereof;

M¹ is a Group 4 metal, preferably zirconium or hafnium;

X¹ is an anionic, neutral or dianionic ligand group;

x′ is a number from 0 to 5 indicating the number of such X¹ groups; and

bonds, optional bonds and electron donative interactions are representedby lines, dotted lines and arrows respectively.

Preferred complexes are those wherein ligand formation results fromhydrogen elimination from the amine group and optionally from the lossof one or more additional groups, especially from R¹². In addition,electron donation from the Lewis base functionality, preferably anelectron pair, provides additional stability to the metal center.Preferred metal complexes correspond to the formula:

wherein

M¹, X¹, x′, R¹¹ and T¹ are as previously defined,

R¹³, R¹⁴, R¹⁵ and R¹⁶ are hydrogen, halo, or an alkyl, cycloalkyl,heteroalkyl, heterocycloalkyl, aryl, or silyl group of up to 20 atomsnot counting hydrogen, or adjacent R¹³, R¹⁴, R¹⁵ or R¹⁶ groups may bejoined together thereby forming fused ring derivatives, and

bonds, optional bonds and electron pair donative interactions arerepresented by lines, dotted lines and arrows respectively.

More preferred examples of the foregoing metal complexes correspond tothe formula:

wherein

M¹, X¹, and x′ are as previously defined,

R¹³, R¹⁴, R¹⁵ and R¹⁶ are as previously defined, preferably R¹³, R¹⁴,and R¹⁵ are hydrogen, or C₁₋₄ alkyl, and R¹⁶ is C₆₋₂₀ aryl, mostpreferably naphthalenyl;

R^(a) independently each occurrence is C₁₋₄ alkyl, and a is 1-5, mostpreferably R^(a) in two ortho-positions to the nitrogen is isopropyl ort-butyl;

R¹⁷ and R¹⁸ independently each occurrence are hydrogen, halogen, or aC₁₋₂₀ alkyl or aryl group, most preferably one of R¹⁷ and R¹⁸ ishydrogen and the other is a C₆₋₂₀ aryl group, especially 2-isopropyl,phenyl or a fused polycyclic aryl group, most preferably an anthracenylgroup, and

bonds, optional bonds and electron pair donative interactions arerepresented by lines, dotted lines and arrows respectively.

Highly preferred metal complexes correspond to the formula:

wherein X¹ each occurrence is halide, N,N-dimethylamido, or C₁₋₄ alkyl,and preferably each occurrence X¹ is methyl;

R^(c), R^(f) and R^(g) independently each occurrence are halogen, C₁₋₂₀alkyl, or C₆₋₂₀ aryl, or two adjacent R^(c), R^(f) or R^(g) groups arejoined together thereby forming a ring, c is and integer from 1 to 4,and f and g, independently is integers from 1-5; and

R^(h) independently each occurrence is hydrogen or C₁₋₆ alkyl.

Additional examples of metal complexes are complexes of the followingformulas:

wherein R^(x) is C₁₋₄ alkyl or cycloalkyl, preferably methyl, isopropyl,t-butyl or cyclohexyl; and

X¹ each occurrence is halide, N,N-dimethylamido, or C₁₋₄ alkyl,preferably methyl.

Examples of such metal complexes include:

-   [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dimethyl;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    di(N,N-dimethylamido);-   [N-(2,6-di(1-methylethyl)phenyl)amido)    o-tolyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dichloride;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dimethyl;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    di(N,N-dimethylamido);-   [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dichloride;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dimethyl;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    di(N,N-dimethylamido);-   [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dichloride;-   [N-[2,6-bis(1-methylethyl)phenyl]-α-[2-(1-methylethyl)phenyl]-6-(1,2-naphthalendiyl-κ-C²)-2-pyridinemethanaminato    (2-)-κN¹,κN²]hafnium dimethyl,-   [N-[2,6-bis(1-methylethyl)phenyl]-α-[2-(1-methylethyl)phenyl]-6-(1,2-naphthalenyl-κ-C²)-2-pyridinemethanaminato    (2-)-κN¹,κN²]hafnium di(n-butyl);-   [N-[2,6-bis(1-methylethyl)phenyl]-α-[2,6-bis(1-methylethyl)phenyl]-6-(1,2-naphthalendiyl-κ-C²)-2-pyridinemethanaminato    (2-)-κN¹,κN²]hafnium dimethyl,-   [N-[2,6-bis(1-methylethyl)phenyl]-α-[2,6-bis(1-methylethyl)phenyl]-6-(1,2-naphthalenyl-κ-C²)-2-pyridinemethanaminato    (2-)-κN¹,κN²]hafnium di(n-butyl)-   [N-[2,6-bis(1-methylethyl)phenyl]-α-[2,6-di(1-methylethyl)phenyl]-5-(2-ethylbenzofuran-3-yl-κ-C⁴)-2-(N′-methyl)imidazol-2-yl)methanaminato    (2-)-κN¹,κN²]hafnium dimethyl,-   [N-[2,6-bis(1-methylethyl)phenyl]-α-[2,6-di(1-methylethyl)phenyl]-5-(2-ethylbenzofuran-3-yl-κ-C⁴)-2-(N′-methyl)imidazol-2-yl)methanaminato    (2-)-κN¹,κN²]hafnium di(n-butyl),-   [N-[2,4,6-tris(1-methylethyl)phenyl]-α-[2,6-di(1-methylethyl)phenyl]-5-(2-ethylbenzofuran-3-yl-κ-C⁴)-2-(N′-methyl)imidazol-2-yl)methanaminato    (2-)-κN¹,κN²]hafnium di(methyl), and-   [N-[2,4,6-tris(1-methylethyl)phenyl]-α-[2,6-bis(1-methylethyl)phenyl]-6-(1,2-naphthalenyl-κ-C²)-2-pyridinemethanaminato    (2-)-κN¹,κN²]hafnium di(n-butyl).

Examples of suitable metal complexes of polyvalent Lewis bases includepolyether compounds corresponding to the formula:

where:

R²⁰ is an aromatic or inertly substituted aromatic group containing from5 to 20 atoms not counting hydrogen, or a polyvalent derivative thereof;

T³ is a hydrocarbylene or silane group having from 1 to 20 atoms notcounting hydrogen, or an inertly substituted derivative thereof;

M³ is a Group 4 metal, preferably zirconium or hafnium;

G is an anionic, neutral or dianionic ligand group; preferably a halide,hydrocarbyl or dihydrocarbylamide group having up to 20 atoms notcounting hydrogen;

g is a number from 1 to 5 indicating the number of such G groups; and

bonds and electron donative interactions are represented by lines andarrows respectively.

Preferably, such complexes correspond to the formula:

wherein:

T³ is a divalent bridging group of from 2 to 20 atoms not countinghydrogen, preferably a substituted or unsubstituted, C₃₋₆ alkylenegroup; and

Ar² independently each occurrence is an arylene or an alkyl- oraryl-substituted arylene group of from 6 to 20 atoms not countinghydrogen;

M³ is a Group 4 metal, preferably hafnium or zirconium;

G independently each occurrence is an anionic, neutral or dianionicligand group;

g is a number from 1 to 5 indicating the number of such X groups; and

electron donative interactions are represented by arrows.

Examples of metal complexes of foregoing formula include the followingcompounds:

where M³ is Hf or Zr;

Ar⁴ is C₆₋₂₀ aryl or inertly substituted derivatives thereof, especially3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl,dibenzo-1H-pyrrole-1-yl, or anthracen-5-yl, and

T⁴ independently each occurrence comprises a C₃₋₆ alkylene group, a C₃₋₆cycloalkylene group, or an inertly substituted derivative thereof;

R²¹ independently each occurrence is hydrogen, halo, hydrocarbyl,trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl of up to 50 atomsnot counting hydrogen; and

G, independently each occurrence is halo or a hydrocarbyl ortrihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2G groups together are a divalent derivative of the foregoing hydrocarbylor trihydrocarbylsilyl groups.

Especially preferred are compounds of the formula:

wherein Ar⁴ is 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl,dibenzo-1H-pyrrole-1-yl, or anthracen-5-yl,

R²¹ is hydrogen, halo, or C₁₋₄ alkyl, especially methyl

T⁴ is propan-1,3-diyl or butan-1,4-diyl, and

G is chloro, methyl or benzyl.

A most highly preferred metal complex of the foregoing formula is:

The foregoing polyvalent Lewis base complexes are conveniently preparedby standard metallation and ligand exchange procedures involving asource of the transition metal and the neutral polyfunctional ligandsource. In addition, the complexes may also be prepared by means of anamide elimination and hydrocarbylation process starting from thecorresponding Group 4 metal tetraamide and a hydrocarbylating agent,such as trimethylaluminum. Other techniques may be used as well. Thesecomplexes are known from the disclosures of, among others, U.S. Pat.Nos. 6,320,005, 6,103,657, WO 02/38628, WO 03/40195, and US04/0220050.

Cocatalysts for Unsaturated Hard Segment Polymer Reagent Synthesis

Generally the foregoing metal complexes are rendered active for olefinpolymerization by contact with an activating cocatalyst. Suitablecocatalysts include those compounds previously known in the art for usewith Group 4 metal olefin polymerization complexes. Examples of suitableactivating cocatalysts include neutral Lewis acids, such as C₁₋₃₀hydrocarbyl substituted Group 13 compounds, especiallytri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds andhalogenated (including perhalogenated) derivatives thereof, having from1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group,more especially perfluorinated tri(aryl)boron compounds, and mostespecially tris(pentafluorophenyl)borane; nonpolymeric, compatible,noncoordinating, ion forming compounds (including the use of suchcompounds under oxidizing conditions), especially the use of ammonium-,phosphonium-, oxonium-, carbonium-, silylium- or sulfonium-salts ofcompatible, noncoordinating anions, or ferrocenium-, lead- or silversalts of compatible, noncoordinating anions; and combinations of theforegoing cation forming cocatalysts and techniques. The foregoingactivating cocatalysts and activating techniques have been previouslytaught with respect to different metal complexes for olefinpolymerizations in the following references: EP-A-277,003, U.S. Pat.Nos. 5,153,157, 5,064,802, 5,321,106, 5,721,185, 5,350,723, 5,425,872,5,625,087, 5,883,204, 5,919,983, 5,783,512, WO 99/15534, and WO99/42467.

Combinations of neutral Lewis acids, especially the combination of atrialkyl aluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to20 carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, further combinations of such neutralLewis acid mixtures with a polymeric or oligomeric alumoxane, andcombinations of a single neutral Lewis acid, especiallytris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxanemay be used as activating cocatalysts. Preferred molar ratios of metalcomplex:tris(pentafluorophenyl-borane:alumoxane are from 1:1:1 to1:5:20, more preferably from 1:1:1.5 to 1:5:10.

Suitable cation forming compounds useful as cocatalysts in oneembodiment of the present invention comprise a cation which is aBronsted acid capable of donating a proton and a compatible,noncoordinating anion, A⁻. As used herein, the term “noncoordinating”means an anion or substance which either does not coordinate to theGroup 4 metal containing precursor complex and the catalytic derivativederived there from, or which is only weakly coordinated to suchcomplexes thereby remaining sufficiently labile to be displaced by aneutral Lewis base. A noncoordinating anion specifically refers to ananion which when functioning as a charge balancing anion in a cationicmetal complex does not transfer an anionic substituent or fragmentthereof to said cation thereby forming neutral complexes. “Compatibleanions” are anions which are not degraded to neutrality when theinitially formed complex decomposes and are noninterfering with desiredsubsequent polymerization or other uses of the complex.

Preferred anions are those containing a single coordination complexcomprising a charge-bearing metal or metalloid core which anion iscapable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitriles. Suitable metals include,but are not limited to, aluminum, gold and platinum. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, and silicon.Compounds containing anions which comprise coordination complexescontaining a single metal or metalloid atom are, of course, well knownand many, particularly such compounds containing a single boron atom inthe anion portion, are available commercially.

Preferably such cocatalysts may be represented by the following generalformula:(L*—H)_(g) ⁺(A)^(g−)wherein:

L* is a neutral Lewis base;

(L*—H)⁺ is a conjugate Bronsted acid of L*;

A^(g−) is a noncoordinating, compatible anion having a charge of g−, and

g is an integer from 1 to 3.

More preferably A^(g−) corresponds to the formula: [M′Q₄]⁻;

wherein:

M′ is boron or aluminum in the +3 formal oxidation state; and

Q independently each occurrence is selected from hydride, dialkylamido,halide, hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl,halosubstituted hydrocarbyloxy, and halo-substituted silylhydrocarbylradicals (including perhalogenated hydrocarbyl-perhalogenatedhydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Qhaving up to 20 carbons with the proviso that in not more than oneoccurrence is Q halide. Examples of suitable hydrocarbyloxide Q groupsare disclosed in U.S. Pat. No. 5,296,433.

In a more preferred embodiment, d is one, that is, the counter ion has asingle negative charge and is A⁻. Activating cocatalysts comprisingboron which are particularly useful in addition polymerizations may berepresented by the following general formula:(L*—H)⁺(BQ₄)⁻;wherein:

L* is as previously defined;

B is boron in a formal oxidation state of 3; and

Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-,fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl-group of upto 20 nonhydrogen atoms, with the proviso that in not more than oneoccasion is Q hydrocarbyl.

Preferred Lewis base salts are ammonium salts, more preferablytrialkylammonium salts containing one or more C₁₂₋₄₀ alkyl groups. Mostpreferably, Q is each occurrence a fluorinated aryl group, especially, apentafluorophenyl group.

Illustrative, but not limiting, examples of boron compounds which may beused as an activating cocatalyst in addition polymerizations aretri-substituted ammonium salts such as:

trimethylammonium tetrakis(pentafluorophenyl) borate, triethylammoniumtetrakis(pentafluorophenyl) borate, tripropylammoniumtetrakis(pentafluorophenyl) borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl) borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl) borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl) borate, N,N-dimethylaniliniumn-butyltris(pentafluorophenyl) borate, N,N-dimethylaniliniumbenzyltris(pentafluorophenyl) borate, N,N-dimethylaniliniumtetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl) borate,N,N-dimethylaniliniumtetrakis(4-(triisopropylsilyl)-2,3,5,6-tetrafluorophenyl) borate,N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl) borate,N,N-diethylanilinium tetrakis(pentafluorophenyl) borate,N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate, dimethyloctadecylammonium tetrakis(pentafluorophenyl) borate,methyldioctadecylammonium tetrakis(pentafluorophenyl) borate, dialkylammonium salts such as:

di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate,methyloctadecylammonium tetrakis(pentafluorophenyl) borate,methyloctadodecylammonium tetrakis(pentafluorophenyl) borate, anddioctadecylammonium tetrakis(pentafluorophenyl) borate; tri-substitutedphosphonium salts such as:

triphenylphosphonium tetrakis(pentafluorophenyl) borate,methyldioctadecylphosphonium tetrakis(pentafluorophenyl) borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate;di-substituted oxonium salts such as:

diphenyloxonium tetrakis(pentafluorophenyl) borate, di(o-tolyl)oxoniumtetrakis(pentafluorophenyl) borate, and di(octadecyl)oxoniumtetrakis(pentafluorophenyl) borate; di-substituted sulfonium salts suchas:

di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, andmethylcotadecylsulfonium tetrakis(pentafluorophenyl) borate.

Preferred (L*—H)⁺ cations are methyldioctadecylammonium cations,dimethyloctadecylammonium cations, and ammonium cations derived frommixtures of trialkyl amines containing one or 2 C₁₄₋₁₈ alkyl groups. Aparticularly preferred example of the latter compound is based on acommercially available long chain amine and is referred to as:bis-(hydrogenated tallowalkyl)methylammoniumtetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:(Ox^(h+))_(g)(A^(g−))_(h),wherein:

Ox^(h+) is a cationic oxidizing agent having a charge of h+;

h is an integer from 1 to 3; and

A^(g−) and g are as previously defined.

Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺′ or Pb⁺². Preferred embodimentsof A^(g−) are those anions previously defined with respect to theBronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst comprises a compoundwhich is a salt of a carbenium ion and a noncoordinating, compatibleanion represented by the formula:[C]⁺A⁻wherein:

[C]⁺ is a C₁₋₂₀ carbenium ion; and

A⁻ is a noncoordinating, compatible anion having a charge of −1. Apreferred carbenium ion is the trityl cation, that istriphenylmethylium.

A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:(Q¹ ₃Si)⁺A⁻wherein:

Q¹ is C₁₋₁₀ hydrocarbyl, and A⁻ is as previously defined.

Preferred silylium salt activating cocatalysts are trimethylsilyliumtetrakispentafluorophenylborate, triethylsilyliumtetrakispentafluorophenylborate and ether substituted adducts thereof.Silylium salts have been previously generically disclosed in J. Chem.Soc. Chem. Comm., 1993, 383-384, as well as Lambert, J. B., et al.,Organometallics, 1994, 13, 2430-2443. The use of the above silyliumsalts as activating cocatalysts for addition polymerization catalysts isdisclosed in U.S. Pat. No. 5,625,087.

Certain complexes of alcohols, mercaptans, silanols, and oximes withtris(pentafluorophenyl)borane are also effective catalyst activators.Such cocatalysts are disclosed in U.S. Pat. No. 5,296,433.

A class of cocatalysts comprising non-coordinating anions genericallyreferred to as expanded anions, further disclosed in U.S. Pat. No.6,395,671, may be suitably employed for olefin polymerizations.Generally, these cocatalysts (illustrated by those having imidazolide,substituted imidazolide, imidazolinide, substituted imidazolinide,benzimidazolide, or substituted benzimidazolide anions) may be depictedas follows:

wherein:

A^(*+) is a cation, especially a proton containing cation, andpreferably is a trihydrocarbyl ammonium cation containing one or twoC₁₀₋₄₀ alkyl groups, especially a methyldi (C₁₄₋₂₀ alkyl)ammoniumcation,

Q³, independently each occurrence, is hydrogen or a halo, hydrocarbyl,halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl, (includingmono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms notcounting hydrogen, preferably C₁₋₂₀ alkyl, and

Q² is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)alumane).

Examples of these catalyst activators includetrihydrocarbylammonium-salts, especially, methyldi(C₁₄₋₂₀alkyl)ammonium-salts of:

bis(tris(pentafluorophenyl)borane)imidazolide,bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide,bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide,bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide,bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide,bis(tris(pentafluorophenyl)borane)imidazolinide,bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide,bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide,bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide,bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolinide,bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide,bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide,

bis(tris(pentafluorophenyl)alumane)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide,bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide,bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide,bis(tris(pentafluorophenyl)alumane)imidazolinide,bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolinide,bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide,bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide,bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide, andbis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.

Other activators include those described in PCT publication WO 98/07515such as tris(2,2′,2″-nonafluorobiphenyl)fluoroaluminate. Combinations ofactivators are also suitable, for example, alumoxanes and ionizingactivators in combinations, see for example, EP-A-0 573120, PCTpublications WO 94/07928 and WO 95/14044 and U.S. Pat. Nos. 5,153,157and 5,453,410. WO 98/09996 describes activating catalyst compounds withperchlorates, periodates and iodates, including their hydrates. WO99/18135 describes the use of organoboroaluminum activators. WO 03/10171discloses catalyst activators that are adducts of Bronsted acids withLewis acids. Other activators or methods for activating a catalystcompound are described in for example, U.S. Pat. Nos. 5,849,852,5,859,653, 5,869,723, EP-A-615981, and PCT publication WO 98/32775.

As previously mentioned, suitable activating cocatalysts includepolymeric or oligomeric alumoxanes, especially methylalumoxane (MAO),triisobutyl aluminum modified methylalumoxane (MMAO), orisobutylalumoxane; Lewis acid modified alumoxanes, especiallyperhalogenated tri(hydrocarbyl)aluminum- or perhalogenatedtri(hydrocarbyl)boron modified alumoxanes, having from 1 to 10 carbonsin each hydrocarbyl or halogenated hydrocarbyl group, and mostespecially tris(pentafluorophenyl)borane modified alumoxanes. Suchcocatalysts are previously disclosed in U.S. Pat. Nos. 6,214,760,6,160,146, 6,140,521, and 6,696,379.

The molar ratio of catalyst/cocatalyst employed preferably ranges from1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferablyfrom 1:1000 to 1:1. Alumoxane, when used by itself as an activatingcocatalyst, may be employed in lower quantity (<100:1) than thepredominant catalyst literature, which is generally at least 100 timesthe quantity of metal complex on a molar basis, and more often around1000 times this quantity. Tris(pentafluorophenyl)borane, where used asan activating cocatalyst is employed in a molar ratio to the metalcomplex of from 0.5:1 to 10:1, more preferably from 1:1 to 6:1 mostpreferably from 1:1 to 5:1. The remaining activating cocatalysts aregenerally employed in approximately equimolar quantity with the metalcomplex.

Diene Elastomer Preparation

The foregoing addition polymerization conditions may be employed forpreparation of suitable diene based elastomers used in the presentcross-metathesis, especially where reduced levels of unsaturation and/orlow levels of vinyl (pendant) unsaturation due to 1,2-addition in theresulting elastomers are desired. For such polymers, copolymerization ofthe diene with ethylene or similar olefin under coordinationpolymerization conditions is preferred. In addition, anionicpolymerization conditions are acceptable for use, especially where nocopolymerizable olefin comonomer is employed. For polymerization ofpolar group containing diene monomers and for conjugated dienehomopolymerizations, free radical polymerization conditions may also beused.

The level of unsaturation in the diene polymer (and thus the length ofpolymer segment produced in the metathesis product) may be controlled byhydrogenation or other suitable technique well known to the skilledartisan. Alternatively, an olefin, such as ethylene, or a cyclic olefinsuch as cyclooctene may be employed during the metathesis to decrease orincrease the molecular weight of the metathesis products.

Metathesis Conditions

Once prepared, the unsaturated polymers are contacted with themetathesis catalyst under conditions to cause olefin cleavage andrearrangement of the cleavage products. The various catalystcompositions that have been found to be effective in promoting olefinmetathesis reactions or ring-opening polymerizations of unsaturatedalicyclic monomers are also effective catalyst compositions forpromoting the processes of the present invention. These catalystcompositions may be either heterogeneous or homogeneous with the formerhaving the advantage of being more readily removable from the reactionproducts while the latter are generally more efficient from thestandpoint of catalytic activity.

Examples of suitable catalyst compositions include organic or inorganicderivatives of transition metals selected from Groups 5-10, preferablymolybdenum, tantalum, tungsten, ruthenium, or rhenium, either in theform of solids, dispersions, suspensions, solutions, or neat. In thesolid form, the catalyst or the individual components thereof may besupported on the surface of an inert carrier or support, such as a highsurface area metal oxide, metalloid oxide, metal carbide, metal boride,metal nitride, zeolite or clay. Preferred compounds include ruthenium,molybdenum or tungsten compounds or complexes, especially halides,oxyhalides, tetraorganoammonium tungstates, tetraorganoammoniummolybdenates, Lewis base derivatives thereof, and mixtures of theforegoing.

Examples of suitable homogeneous catalyst compositions employed in thepractice of this invention include those previously disclosed in U.S.Pat. No. 4,010,224, especially compositions comprising: (A) at least oneorganometallic compound wherein the metal is selected from Groups 1, 2,12 or 13 of the Periodic Table of Elements, (B) at least one metalderivative wherein the metal is selected from the group consisting ofmetals of Groups 5, 6, or 7, especially molybdenum or tungsten and,optionally, (C) at least one chelating- or Lewis base-material. Examplesof the latter compounds include ethers, carboxylic acid esters, ketones,aldehydes, carbonates, nitriles, alcohols, thiols, water, and mixturesthereof.

Representative examples of organometallic compounds from which component(A) may be selected include lithium, sodium, potassium, rubidium,cesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium,aluminum, gallium, indium, and thallium compounds, with lithium, sodium,magnesium, aluminum, zinc and cadmium compounds being preferred and withaluminum compounds being most preferred.

Representative examples of organometallic compounds useful as catalystcomponent (A) are organoaluminum compounds having at least onealuminum-to-carbon bond. Representative of such compounds aretri(C₁₋₁₀)hydrocarbylaluminum compounds such as trimethylaluminum,triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum,triisopropylaluminum, triisobutylaluminum, trihexylaluminum,trioctylaluminum, tritolylaluminum, tribenzylaluminum, andtriphenylaluminum; organoaluminum halides such as diethylaluminumchloride, di-n-propylaluminum chloride, diisobutylaluminum chloride,diethylaluminum bromide, diethylaluminum iodide and diethylaluminumfluoride, ethylaluminum dichloride, ethylaluminum sesquichloride,ethylaluminum dibromide, propylaluminum dichloride, isobutylaluminumdichloride, ethylaluminum diiodide, phenylaluminum dibromide,tolylaluminum dibromide, benzylaluminum dibromide, phenylaluminumdiiodide, tolylaluminum diiodide, benzylaluminum diiodide,diphenylaluminum chloride, ditolylalumium chloride, and dibenzylaluminumbromide; organoaluminum hydride compounds such as diphenylaluminumhydride and phenylaluminum dihydride; and mixtures of the foregoing.

Additional suitable organometallic compounds are alkali metal compoundssuch as ethyllithium, n-butyllithium, t-butyllithium, amylsodium,butylpotassium, phenylpotassium, phenylsodium, phenyllithium,lithium-aluminum tetrabutyl, lithium-aluminum tetraethyl,lithium-aluminum triethyl chloride, and sodium aluminum tetraethyl;alkaline earth metal compounds such as diphenylmagnesium,diethylmagnesium, ethylmagnesium chloride, phenylmagnesium chloride,butylmagnesium bromide, butyl calcium chloride, and diethylbarium; Group12 organometal compounds such as diethylzinc, diphenylzinc, ethylzincchloride, diethylcadmium, and dibutyl-cadmium; phenylmagnesium bromide,butylmagnesium chloride, butylmagnesium bromide, and ethylmagnesiumchloride; and mixtures of the foregoing compounds. Preferred compoundsfor use as component (A) are trialkylaluminums, dialkylaluminum halides,alkylaluminum dihalides and aluminumsesquihalides, containing up to 4carbons in each alkyl group.

Suitable derivatives of molybdenum and tungsten useful as component (B)of the metathesis catalyst include the corresponding halides-,acetylacetonates-, sulphates-, phosphates-, nitrates-, and alcoholates.Examples include: chlorides, bromides, iodides and fluorides, such asmolybdenum pentachloride, tungsten hexachloride, molybdenumpentabromide, tungsten hexabromide, molybdenum pentaiodide, molybdenumpentafluoride, molybdenum hexafluoride and tungsten hexafluoride. Otherexamples include molybdenum phosphate, tungsten phosphate, molybdenumnitrate, tungsten nitrate, molybdenum acetylacetonate, tungstenacetylacetonate, molybdenum sulphate, and tungsten sulphate. Mixtures ofthese compounds may also be employed. The tungsten- and molybdenumhalides, representative of which are tungsten hexachloride andmolybdenum pentachloride, are especially preferred.

Suitable compounds for use as component (C) of the catalyst compositionare compounds of the general formula R—Y—H wherein Y is selected fromthe group of oxygen and sulfur and wherein R is hydrogen, or ahydrocarbyl or substituted hydrocarbyl group having up to 20 carbonstotal, and wherein the substituent(s) on the hydrocarbyl group areselected from the group consisting of hydroxy, thio, hydrocarbyloxy,hydrocarbylthio, oxy- and sulfo-. Examples include water, hydrogensulfide, alkanols, aromatic alcohols, mercaptans, hydrocarbylperoxides,polyalcohols, polymercaptans, hydroxy mercaptans, alkanolethers,alkanolthioethers, mercaptoethers and mercaptothioethers. Representativeexamples of the materials for use as component (C) include alcohols suchas methanol, ethanol, isopropanol, tertiarybutyl alcohol, amyl alcohol,benzyl alcohol, allyl alcohol, 1,1-dimethyl benzyl alcohol, phenol,tertiarybutyl catechol, cresol, alpha and beta naphthyl alcohol;mercaptans such as methyl-, ethyl-, propyl-, isopropyl-, butyl-, amyl-or allylmercaptan, thiophenol, 4-methylthiophenol, or 4-mercaptophenol;hydroperoxides, such as, cumyl hydroperoxide, tertiarybutylhydroperoxide; hydrodisulfides such as cumyl hydrodisulfide, and s-butylhydrodisulfide; polyalcohols, such as ethylene glycol, glycerol,polyethyleneglycol, catechol, resorcinol, hydroquinone, pyrogallol;polymercaptans, such as 1,3-propane dithiol, 1,4-dithiobenzene; andhydroxymercaptans, such as, 1-hydroxy-2-thioethane or1-hydroxy-4-thiobenzene.

The quantity of component (C) employed in the foregoing catalystcomposition is adjusted to control the activity of the catalystcomposition. Generally, the catalyst composition exhibits higheractivity when the quantity of component (C) employed is relativelysmall, including none.

Generally the quantities of the respective catalyst components areadjusted to be within a molar ratio of (B)/(C) ranging from 0.3/1 to20/1 and the molar ratio of (A)/(B) is within the range of 0.5/1 to15/1. More preferred ratios of (B)/(C) are from 0.5/1 to 5/1 and (A)/(B)from 0.5/1 to 8/1. Still more preferred ratios of (B)/(C) are 1/1 to 2/1and (A)/(B) are 0.75/1 to 5/1.

The foregoing catalyst compositions may be prepared by mixing thecomponents by known techniques, either prior to combination with theolefin containing polymer or “in situ”. By the “preformed” method thecatalyst components are mixed together prior to exposure of any of thecatalyst components to the olefin containing polymer to be used in theprocess of this invention. In the “in situ” method the catalystcomponents are added separately to the reaction mixture containing theunsaturated polymer to be subjected to metathesis. The catalystcomponents may be mixed either as pure compounds or as suspensions orsolutions in liquids which do not adversely affect the catalyst activityof the olefin metathesis reaction. Representative of such liquids aresaturated hydrocarbons such as hexane, pentane, benzene, toluene ormixtures thereof.

The order of addition of the three catalyst components to each other maybe varied. All of the following practices may suitably be employed:

1. simultaneous addition of components (A), (B) and (C);

2. sequential addition of components (A), (B) and (C) in any order;

3. contacting of any two components, optionally with recovery orpurification of the reaction product, followed by addition of the binaryproduct to the remaining component; or

4. contacting of mixtures of any two components with subsequent contactof the resulting binary mixtures or reaction products, whether purifiedor unpurified.

In one preferred embodiment, the catalyst composition comprises at leastone organoaluminum halide and at least one tungsten derivative.Preferred organoaluminum halides are dialkylaluminum chloride,di-n-propylaluminum chloride, diisobutyolaluminum chloride,diethylaluminum bromide, diethylaluminum iodide, diethylaluminumfluoride, ethylaluminum sesquichloride, ethylaluminum sesquibromide,ethylaluminum dichloride, ethylaluminum dibromide, propylaluminumdichloride, isobutylaluminum dichloride, ethylaluminum diiodide,phenylaluminum dibromide, tolylaluminum dibromide, benzylaluminumdibromide, phenylaluminum diiodide, tolylaluminum diiodide,benzylaluminum diiodide, diphenylaluminum chloride, ditolylaluminumchloride, dibenzylaluminum bromide, and mixtures of the foregoing.

Preferred tungsten derivatives include halides-, sulfates-, phosphates-,nitrates- and carboxylates- of tungsten in the +4 or +6 oxidation state,preferably tungsten hexachloride, tungsten hexabromide, tungstenhexaiodide, tungsten hexafluoride, tungsten diphosphate, tungstenhexanitrate, tungsten triacetylacetonate, tungsten oxychloride, andtungsten trisulphate. A most preferred tungsten derivative is tungstenhexachloride.

The molar relationship between the two catalyst components in thisembodiment are generally from 0.5/1 to 15/1, more preferably from 0.7/1to 8/1, and a still more preferably from 0.8/1 to 5/1. The catalystcomponents may be reacted together as pure compounds or in solutions orsuspensions in inert, aliphatic or aromatic liquids. Representative ofsuch liquids are pentane, hexane, benzene, and toluene.

A third catalyst composition that is effective in promoting the presentmetathesis process comprises an aluminum trihalide and an organic orinorganic derivative of a Group 5, 6 or 7 compound, preferably atungsten compound, especially those wherein the tungsten is in anoxidation state from 4 to 6. The preferred aluminum trihalides arealuminum trichloride or aluminum tribromide. Preferred tungstencompounds are tetra-, penta- and hexa-chlorides, bromides, and iodides,tungsten hexafluoride and the tungsten oxychlorides. Optionally anorganometallic compound may be present in the catalyst composition as anaid in the suppression of gel formation and in order to increasepolymerization rates at lower catalyst levels. Examples of suitableoptional organometallic compounds include alkyl-, aryl-, and alkarylderivatives of lithium, sodium, magnesium, calcium, strontium andbarium; alkylhalide-, arylhalide-, and alkarylhalide derivatives ofmagnesium, calcium, strontium or barium and alkyl-, aryl- oralkaryl-derivatives of Group 12 metals such as dialkyl- and diarylzinc,said alkyl, aryl or alkaryl group having up to 10 carbons.

Other classes of catalysts which are effective in promoting thepolymerizations of this invention are those disclosed in U.S. Pat. No.4,994,535, and generally include an organometal derivative of a Group13-14 metal, especially organo- or organohalo-derivatives of aluminum ortin, preferably tetraalkyl tin, trialkyl aluminum and dialkylaluminumhalides, containing up to 10 carbons in each alkyl group; at least onederivative of a Group 5, 6, or 7 metal, especially molybdenum ortungsten; and optionally, a chelating agent, such as a Lewis base.

Additional suitable metathesis catalysts for use in the presentinvention are ruthenium or osmium complexes such as those disclosed inU.S. Pat. Nos. 6,838,489, 6,818,586, 6,806,325, 6,624,265, 6,313,332,5,977,393, 5,917,071, 5,710,298, 5,750,815, 5,728,917, 5,312,940, and5,342,909. Examples of the foregoing metathesis catalysts includeruthenium and osmium carbene complexes possessing metal centers that areformally in the +2 oxidation state, have an electron count of 16, andare penta-coordinated. These complexes are of the general formula:

wherein:

M^(A) is ruthenium or osmium;

X^(A) and X^(B) are the same or different anionic ligands, preferablychloride;

L^(A) is a neutral electron donor ligand;

L^(B) is a neutral electron donor ligand or a nitrogen containingheterocyclic carbene; and

R^(A) and R^(B) are independently each occurrence hydrogen, or an alkyl,alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy,aryloxy, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkylsulfinyl, orsilyl group of up to 20 atoms not counting hydrogen, an alkyl, alkoxy,aryl, aralkyl, haloalkyl, haloalkoxy, haloaryl or haloalkarylsubstituted derivative thereof; or a functionalized derivative of any ofthe foregoing wherein the functional group is hydroxyl, thiol, alcohol,sulfonic acid, phosphine, thioether, ketone, aldehyde, ester, ether,amine, imine, amide, imide, imido, nitro, carboxylic acid, disulfide,carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, acetal,ketal, boronate, cyano, cyanohydrin, hydrazine, oxime, hydrazide,enamine, sulfone, sulfide, sulfenyl, or halogen.

In a preferred embodiment, the metal complexes are ruthenium derivativeswherein L^(B) is a tertiary phosphine, especially triphenylpsphine, andL^(A) is either a tertiary phosphine or a nitrogen containingheterocyclic ligand, especially an imidazolidinyl- or triazolyl-ligandof the formula:

wherein Ar independently each occurrence is an aryl group, especiallyphenyl or 2,4,6-trimethylphenyl, and R^(C) independently each occurrenceis hydrogen or an anionic ligand group or multiple R^(C) groupscollectively may form one or more rings that are fused to theimidazolidine ring.

The inclusion of an imidazolidinyl or triazoyl ligand to the previouslydescribed ruthenium or osmium catalysts improves the properties of thecomplexes in olefin metathesis processes. In particular, the catalystsmaintain the general functional group tolerance towards olefins ofruthenium-phosphine complexes while possessing enhanced metathesisactivity comparable to tungsten- and molybdenum-salt ternarycompositions. Such catalysts (referred to as Grubbs II catalysts) areparticularly desired for metathesis of polar group containing polymers.

The operating conditions which are employed in the processes of thisinvention may vary. The reactions can be conveniently carried out in aliquid form, including in a melt, or even in the solid phase, such asthe previously disclosed surface depolymerizing system. Thus, when apolymeric material is employed in any particular reaction, it ispossible to carry out the reaction in solution, in a melt or as a“swollen” solid, employing solvent to enter the polymer matrix and/orpartially dissolve the polymer or the depolymerized reaction productsfrom the metathesis. Solvents which can be used when solution conditionsare employed include any inert liquid that dissolves or swells thepolymers employed. Convenient solvents are aliphatic, aromatic orcycloaliphatic hydrocarbons which do not themselves inhibit or interferewith the metathesis reaction, such as pentane, hexane, benzene, toluene,and cyclohexane. When one or more of the olefin reactants is a liquid,the reaction can be conducted in bulk, that is, in the absence of aseparately added solvent.

A small quantity of ethylene may be included in the reaction mixture, asis known in the art, for purposes of reducing the molecular weight ofone or more of the ethylenically unsaturated monomers prior tometathesis. Generally, the quantity of ethylene employed is from 0.5 to10 moles, preferably from 0.5 to 2 moles, per mole of metathesiscatalyst.

The amount of metathesis catalyst employed in the reactions of thisinvention may be varied over wide concentrations and has not been foundto be critical. The optimum amount of catalyst composition employeddepends upon a number of factors such as temperature, purity ofreactants, and the desired reaction time. The catalyst is desirablyemployed in an amount (based on weight of transition metal component)from 0.01 to 1 percent based on weight of unsaturated polymer.

Metathesis process conditions may vary widely over any operableconditions suitable for preparing the polymer compositions of thisinvention. Any temperature below the decomposition temperatures of thereactant polymers, product polymer(s), and metathesis catalyst, andpreferably below the normal boiling point of any solvent or diluent, ifused, is generally suitable. When the metathesis is conducted in a neatpolymer melt, the process temperature may broadly range from about 100°C. up to about 350° C., depending upon the decomposition temperatures asnoted hereinbefore. Generally, a temperature of about 20° C. to 50° C.above the polymer melt or glass transition temperature is preferred.When the metathesis is conducted with the reactant polymers dissolved ina liquid diluent or solvent, the temperature may typically range fromabout 25° C. up to about 150° C. Preferred temperatures for use with thepreferred Grubbs catalysts range from about 35° C. up to about 100° C.,more preferably, up to about 85° C. Typically, a process pressure ofabout 1 atmosphere is suitable, but higher and lower pressures may beemployed if desired. Metathesis processes reach an equilibrium, thusconversion of the reactant polymers is typically incomplete. Samples maybe taken from the reaction mixture and analyzed via CRYSTAF or ATREF,for example, to determine when the equilibrium conversion is reached.The metathesis reaction can be stopped at any time prior to reachingequilibrium conversion to obtain different distributions of productpolymers.

Once the metathesis has proceeded to the extent desired, the catalystmay be inactivated, and if desired, the resulting polymer may behydrogenated to remove residual unsaturation. Suitable methods ofinactivating the metathesis catalyst include reaction with water; analcohol; a carboxylic acid, or a metal salt or ester derivative thereof;or carbon monoxide. The resulting catalyst residue may be removed fromthe polymer by filtration, solvent extraction, or other suitabletechnique, or may be left in the polymer. Suitable hydrogenationcatalysts include those previously known in the art, especially noblemetal catalysts such as platinum or palladium containing compounds orcomplexes.

EXAMPLES

It is understood that the present invention is operable in the absenceof any component which has not been specifically disclosed and may becombined with any other suitable reaction or process in a multistepsystem design. The following examples are provided in order to furtherillustrate the invention and are not to be construed as limiting. Unlessstated to the contrary, all parts and percentages are expressed on aweight basis.

In the examples hereinafter, the term “Grubbs II catalyst” refers to ametathesis catalyst consisting ofbenzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium.

All metathesis reactions are conducted under an inert atmosphere ofnitrogen gas.

Unsaturated Reagent Polymers

In the following preparations, the unsaturation level of the reagentpolymer is calculated from ¹H NMR spectral data.

Polybutadiene (PBD) (2 percent 1,2-vinyl, 98 percent cis1,4-polymerization, approximate Mw=250,000 g/mol, available fromScientific Polymer Products). Ethylenic carbon content=42 percent.

Hydrogenated Polybutadiene (HPBD) PBD is partially hydrogenatedsubstantially according to the procedure described in J. Polym. Sci.Polym. Chem., 1992, 30, 397-408. Accordingly, a 2 percent solution isprepared by dissolving PBD in o-xylene and heating to 95° C. followed bythe addition of p-toluenesulfonyl hydrazide (TSH) and tri(n-propyl)amineTPA (1.1 moles per mole unsaturation for both TSH and TPA). Afterrefluxing for 4 hours, the solution is cooled to room temperature andprecipitated by addition to methanol. The dried filtered solid isre-precipitated by dissolving in warm toluene and adding to methanol.Hydrogenation level is 90 percent as determined by ¹H NMR spectrographicanalysis. Unsaturation level is 5.5 mole percent. Tm=109° C.

Hydrogenated nitrile/butadiene rubber (HNBR) A partially hydrogenatedacrylonitrile/butadiene random copolymer (hydrogenation of ethylenicunsaturation approximately 90 percent), having acrylonitrile content of33 percent and a Mooney-Viscosity UML (1+4)@100° C. of 61 (THERBAN™3467, available from Lanxess, Inc). Tg=−25° C. Unsaturation level is0.81 mole percent.

Ethylene/1-octene/Butadiene Copolymer Copolymerizations of mixtures ofethylene and 1-octene with butadiene are conducted in a computercontrolled 2 L Parr batch reactor, which is heated by an electricalheating mantle and cooled by an internal serpentine cooling coil withchilled water. The bottom of the reactor is fitted with a stainlesssteel ball valve which empties the reactor contents into a stainlesssteel vessel containing a toluene solution of a standard stabilizer andantioxidant. The polymer mixture is purged with nitrogen for 20 minutesafter discharge into the collection vessel.

All chemicals and catalysts are manipulated in a nitrogen-filled drybox.The 1-octene, butadiene and mixed hexanes solvent (Isopar™ E, availablefrom ExxonMobil Chemicals, Inc.) are purified by passage through alumna(8×14 A2 alumna, available from UOP Corporation) then a catalyst (Q5™reactant, available from Engelhard Corporation). Ethylene is passedthrough a first column containing alumina (A204™ available from LaRouch,Inc.) followed by 0.4 nm molecular sieves and then through a secondcolumn containing Q5™ reactant. The nitrogen used for all transfers ispassed through a single column containing A204 alumna, 0.4 nm molecularsieves and Q5™ reactant.

The reactor is charged from a shot tank containing a pre-weighedquantity of mixed alkanes (700 g) and 1-octene (20 g). The shot tank isfilled to the desired level by use of a laboratory scale upon which thetank is mounted. Butadiene is loaded using a computer operatedcontroller (Emerson Micro Motion™ controller). After solvent, butadieneand 1-octene addition, the reactor is heated to the polymerizationtemperature and ethylene is added to achieve the desired pressure of 3.4MPa.

The catalyst((t-butylamido)dimethyl(1H-cyclopenta[l]-phenanthrene-2-yl)silanetitanium(IV) dimethyl, prepared according to U.S. Pat. No. 6,150,297),triethyl aluminum scavenger and activator (methyldi(octadecyl)ammoniumtetrakis(pentafluorophenyl)borate) are combined in the stated order intoluene under nitrogen atmosphere. This mixture is drawn into a syringeand pressure transferred into the catalyst shot tank, followed by three5 mL rinses of toluene. After charging the catalyst solution to thereactor, ethylene is supplied on demand at 3.4 MPa until the reaction isterminated.

Polymerizations are conducted for 10 minutes and then the reactorcontents are discharged to the collection vessel. After purging withnitrogen, the polymer solution is poured into a tray and placed in a labhood overnight to evaporate solvent. The trays are then transferred to avacuum oven and heated at 145° C. under reduced pressure to remove anyremaining solvent. A total polymer yield of 42 g is obtained afterevaporation of the volatile components. GPC analysis reveals Mw=200,000and Mn=90,000 Daltons. NMR analysis reveals that 95 percent of thedouble bonds are in the backbone of the polymer chain with 5 percentside-chain vinyl content and a 1-octene content of 8.5 mole percent.

A poly(ethylene-co-butadiene) is so prepared having 2.1 mole percentunsaturation and a melting transition of 126° C.

A poly(ethylene-co-butadiene-co-octene) is so prepared having 0.38 molepercent unsaturation and a glass transition of −38° C.

Polycyclo-octene (PCO) Cyclo-octene (10 ml of a 1 M toluene solution) iscontacted with 0.1 mole percentbenzylidene-bis(tricyclohexylphosphine)dichlororuthenium and theresulting mixture is heated at 55° C. for 2 hours followed by additionof butyl vinyl ether (10 mmol). The solution is cooled and precipitatedby addition to methanol. The weight average molecular weight of theresulting polymeric product is 289,000 g/mol as determined by GPC (PSstandard). Ethylene carbon content is 21.8 weight percent.

Bisphenol-A Polycarbonate, Modified with Furmaryl Chloride Bisphenol-Apolycarbonate modified with fumaryl chloride, such that amonomer/terminator ratio of 16/1, is prepared according to the followingprocedure.

A. Preparation of Solutions: Aqueous Alkaline Bisphenol-A Solution:Bisphenol-A (BisA) (6.5 g, 27 mmole) is weighed into a 100 ml glassbottle. The bottle is flushed with nitrogen. Then, 50 ml of 1.5 mole/lsodium hydroxide solution (75 mmole NaOH) are added. The bottle isflushed with nitrogen again. The bisphenol is dissolved under slightagitation by means of a magnetic stirrer.

Triethyl Amine (Coupling Catalyst Solution): Triethylamine (2.0 g) isweighed into a 250 ml glass bottle. Dichloromethane (150 ml) is addedand the resulting mixture is shaken to form a homogenous solution. Thebottle is connected to a Schott automatic dispenser from which a buretteis filled with the solution.

Terminator Solution: para-Tertiary butylphenol (PTBP) (0.281 g; 1.87mmole) is weighed into a 100 ml glass bottle. Dichloromethane (50 ml) isadded. After the terminator is dissolved by slightly shaking, the bottleis connected to a Schott automatic dispenser from which a burette isfilled with the solution.

Triphosgene Solution Bis(trichloromethyl)carbonate (triphosgene; 4.5 g)is weighed into a 250 ml glass bottle, filled up with 45 mldichloromethane, and completely dissolved by slightly shaking thebottle. The glass bottle with the triphosgene solution is connected to aSchott automatic dispenser from which a burette is filled with thesolution.

B. Synthesis: A jacketed reactor is temperature controlled by a waterbath at the desired temperature of 35° C. The reactor is flushed withnitrogen. The bisphenol-A solution is filled into the reactor. Theagitator is started and kept at 300 rpm. The cooling water of thecondenser is turned on. Dichloromethane (20 ml) is added. The pH isadjusted at 13 (+/−0.1) by addition of 32 wt percent aqueous HCl. Thetriphosgene solution (27 ml) is added within 2 minutes. The resultingmixture is reacted for 30 minutes. The pH is adjusted to a value of 9 byaddition of 15 wt percent aqueous HCl. Fumaryl chloride (0.23 g) isadded by syringe. The mixture is reacted for 10 minutes. The pH isincreased to a value of 12.5 by addition of 20 wt percent aqueous NaOH.Terminator solution (10 ml) is added all at once. Triphosgene solution(11 ml) is added over 2 minutes. The resulting mixture is reacted for 30minutes. Triethylamine solution (30 ml) is added. NaOH solution (3 ml 30wt %) is added. The resulting mixture is reacted for another 10 minduring which time the pH is kept at 12.5 by addition of further 20 wtpercent NaOH.

C. Polymer Purification: An emulsion of organic and aqueous phasesobtained from the above synthesis is released into a 250 ml beaker, andthen the liquid is filled into a 250 ml separating funnel. The lighteraqueous phase is removed by decantation. The heavier organic phasecontaining the polymer solution is filled back into the separatingfunnel and mixed thoroughly with 100 ml 2 molar aqueous HCl. Next, thepolymer phase is separated into a 250 ml beaker. The aqueous phase isremoved. The polymer is filled into a separating funnel and the HCl washis repeated. Then, the polymer is washed four times with 100 mldeionized water, each time in a manner similar to the acid washes. Theresulting pure polymer solution is filled into an aluminum pan, which iswarmed on an electrical heating disk to remove dichloromethane byevaporation. The resulting solid polymer, an unsaturated polycarbonate,is dried at 100° C. and 10 mbar for 12 hours. The modified polycarbonatehas the following properties: Mw, 27.5 g/mol (vs PS standards); PDI,3.89; 10.5 mole percent (4 wt percent) fumaryl incorporated.Unsaturation level is 1.5 mole percent; Tg, 144° C.

Polyethylene oxide) A stirred mixture of 50.0 grams poly(ethyleneglycol) (average Mn 380-420 g/mol), 8.82 grams dimethyl maleate and 10.3grams isophthalic acid is added to a flask and flushed with nitrogen.The mixture is heated to 165° C. and 1500 ppm monobutyltin oxidecatalyst is added. After 2 hours, the flask is placed under vacuum for 2additional hours and cooled to yield an unsaturated poly(ethylene oxide)polymer. Tg=−54.3° C. Mw=7,570 g/mol, Mw/Mn=4.33 (vs. polystyrenestandards). Unsaturation level is 4.9 mole percent.

Analytical

In the foregoing characterizing disclosure and the example that follows,the following analytical techniques may be employed:

SAXS

Small angle x-ray scattering (SAXS) experiments are conducted at theAdvanced Photon Source (APS), DND-CAT, 5-ID-D beamline. The standard APSUndulator A was used as the x-ray source, with the x-ray energy set at15 keV (λ=0.82656 Å). Two-dimensional scattering patterns are collectedon a MARUSA, Inc. CCD camera with a collection data acquisition time setat 1 sec. Angular calibration of the detectors is achieved using silverbehenate standards. The sample to detector distance is set at 531.9 cm.Two dimensional scattering patterns are reduced to one dimensional datasets of scattering intensity versus scattering angle by radialintegration of the 2-D images, using a data visualization and analysissoftware package on the PV-WAVE platform. Reduction and analysis of theone dimensional patterns is performed JADE™ analysis software. DSCanalysis is conducted on approximately 20 mg of sample loaded intoaluminum DSC pans. Sample pans are sealed with an aluminum lid. DSCexperiments are performed using a Linkam™ DSC cell. Samples are heatedfrom 20 to 300° C. at 10° C./minute, then cooled to 20° C. at a coolingrate of 10° C./min. SAXS patterns are collected during the thermal cycleat 2° C. intervals.

CRYSTAF

Branching distributions are determined by crystallization analysisfractionation (CRYSTAF) using a CRYSTAF 200 unit commercially availablefrom PolymerChar, Valencia, Spain. The samples are dissolved in 1,2,4trichlorobenzene at 160° C. (0.66 mg/mL) for 1 hr and stabilized at 95°C. for 45 minutes. The sampling temperatures range from 95 to 30° C. ata cooling rate of 0.2° C./min. An infrared detector is used to measurethe polymer solution concentrations. The cumulative solubleconcentration is measured as the polymer crystallizes while thetemperature is decreased. The analytical derivative of the cumulativeprofile reflects the short chain branching distribution of the polymer.

The CRYSTAF peak temperature and area are identified by the peakanalysis module included in the CRYSTAF Software (Version 2001.b,PolymerChar, Valencia, Spain). The CRYSTAF peak finding routineidentifies a peak temperature as a maximum in the dW/dT and the areabetween the largest positive inflections on either side of theidentified peak in the derivative curve. To calculate the CRYSTAF curve,the preferred processing parameters are with a temperature limit of 70°C. and with smoothing parameters above the temperature limit of 0.1, andbelow the temperature limit of 0.3.

DSC Standard Method

Differential Scanning Calorimetry results are determined using a TAImodel Q1000 DSC equipped with an RCS cooling accessory and anautosampler. A nitrogen purge gas flow of 50 ml/min is used. The sampleis pressed into a thin film and melted in the press at about 175° C. andthen air-cooled to room temperature (25° C.). 3-10 mg Of material isthen cut into a 6 mm diameter disk, accurately weighed, placed in alight aluminum pan (ca 50 mg), and then crimped shut. The thermalbehavior of the sample is investigated with the following temperatureprofile. The sample is rapidly heated to 180° C. and held isothermal for3 minutes in order to remove any previous thermal history. The sample isthen cooled to −40° C. at 10° C./min cooling rate and held at −40° C.for 3 minutes. The sample is then heated to 150° C. at 10° C./min.heating rate. The cooling and second heating curves are recorded.

The DSC melting peak is measured as the maximum in heat flow rate (W/g)with respect to the linear baseline drawn between −30° C. and end ofmelting. The heat of fusion is measured as the area under the meltingcurve between −30° C. and the end of melting using a linear baseline.

GPC

The gel permeation chromatographic system consists of either a PolymerLaboratories Model PL-210 or a Polymer Laboratories Model PL-220instrument. The column and carousel compartments are operated at 140° C.Three Polymer Laboratories 10-micron Mixed-B columns are used. Thesolvent is 1,2,4 trichlorobenzene. The samples are prepared at aconcentration of 0.1 grams of polymer in 50 milliliters of solventcontaining 200 ppm of butylated hydroxytoluene (BHT). Samples areprepared by agitating lightly for 2 hours at 160° C. The injectionvolume used is 100 microliters and the flow rate is 1.0 ml/minute.

Calibration of the GPC column set is performed with 21 narrow molecularweight distribution polystyrene standards with molecular weights rangingfrom 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least adecade of separation between individual molecular weights. The standardsare purchased from Polymer Laboratories (Shropshire, UK). Thepolystyrene standards are prepared at 0.025 grams in 50 milliliters ofsolvent for molecular weights equal to or greater than 1,000,000, and0.05 grams in 50 milliliters of solvent for molecular weights less than1,000,000. The polystyrene standards are dissolved at 80° C. with gentleagitation for 30 minutes. The narrow standards mixtures are run firstand in order of decreasing highest molecular weight component tominimize degradation. The polystyrene standard peak molecular weightsare converted to polyethylene molecular weights using the followingequation (as described in Williams and Ward, J. Polym. Sci., Polym.Let., 6, 621 (1968)): M_(polyethylene)=0.431 (M_(polystyrene)).

Polyethylene equivalent molecular weight calculations are performedusing Viscotek TriSEC software Version 3.0.

Compression Set

Compression set is measured according to ASTM D 395. The sample isprepared by stacking 25.4 mm diameter round discs of 3.2 mm, 2.0 mm, and0.25 mm thickness until a total thickness of 12.7 min is reached. Thediscs are cut from 12.7 cm×12.7 cm compression molded plaques moldedwith a hot press under the following conditions: zero pressure for 3 minat 190° C., followed by 86 MPa for 2 min at 190° C., followed by coolinginside the press with cold running water at 86 MPa.

Density

Samples for density measurement are prepared according to ASTM D 1928.Measurements are made within one hour of sample pressing using ASTMD792, Method B.

Flexural/Secant Modulus/Storage Modulus

Samples are compression molded using ASTM D 1928. Flexural and 2 percentsecant moduli are measured according to ASTM D-790. Storage modulus ismeasured according to ASTM D 5026-01 or equivalent technique.

Optical Properties

Films of 0.4 mm thickness are compression molded using a hot press(Carver Model #4095-4PR1001R). The pellets are placed betweenpolytetrafluoroethylene sheets, heated at 190° C. at 55 psi (380 kPa)for 3 min, followed by 1.3 MPa for 3 min, and then 2.6 MPa for 3 min.The film is then cooled in the press with running cold water at 1.3 MPafor 1 min. The compression molded films are used for opticalmeasurements, tensile behavior, recovery, and stress relaxation.

Clarity is measured using BYX Gardner Haze-gard as specified in ASTM D1746.

45° gloss is measured using BYK Gardner Glossmeter Microgloss 45° asspecified in ASTM D-2457

Internal haze is measured using BYK Gardner Haze-gard based on ASTM D1003 Procedure A. Mineral oil is applied to the film surface to removesurface scratches.

Mechanical Properties—Tensile, Hysteresis, and Tear

Stress-strain behavior in uniaxial tension is measured using ASTM D 1708microtensile specimens. Samples are stretched with an Instron at 500%min⁻¹ at 21° C. Tensile strength and elongation at break are reportedfrom an average of 5 specimens.

100% and 300% Hysteresis is determined from cyclic loading to 100% and300% strains using ASTM D 1708 microtensile specimens with an Instron™instrument. The sample is loaded and unloaded at 267% min⁻¹ for 3 cyclesat 21° C. Cyclic experiments at 300% and 80° C. are conducted using anenvironmental chamber. In the 80° C. experiment, the sample is allowedto equilibrate for 45 minutes at the test temperature before testing. Inthe 21° C., 300% strain cyclic experiment, the retractive stress at 150%strain from the first unloading cycle is recorded. Percent recovery forall experiments are calculated from the first unloading cycle using thestrain at which the load returned to the base line. The percent recoveryis defined as:

${\%\mspace{14mu}{Recovery}} = {\frac{ɛ_{f} - ɛ_{s}}{ɛ_{f}} \times 100}$

where ∈_(r) is the strain taken for cyclic loading and ∈_(s) is thestrain where the load returns to the baseline during the 1^(st)unloading cycle.

Stress relaxation is measured at 50 percent strain and 37° C. for 12hours using an Instron™ instrument equipped with an environmentalchamber. The gauge geometry was 76 mm×25 mm×0.4 mm. After equilibratingat 37° C. for 45 min in the environmental chamber, the sample wasstretched to 50% strain at 333% min⁻¹. Stress was recorded as a functionof time for 12 hours. The percent stress relaxation after 12 hours wascalculated using the formula:

${\%\mspace{14mu}{Stress}\mspace{14mu}{Relaxation}} = {\frac{L_{0} - L_{12}}{L_{0}} \times 100}$where L₀ is the load at 50% strain at 0 time and L₁₂ is the load at 50percent strain after 12 hours.

Tensile notched tear experiments are carried out on samples having adensity of 0.88 g/cc or less using an Instron™ instrument. The geometryconsists of a gauge section of 76 mm×13 mm×0.4 mm with a 2 mm notch cutinto the sample at half the specimen length. The sample is stretched at508 mm min⁻¹ at 21° C. until it breaks. The tear energy is calculated asthe area under the stress-elongation curve up to strain at maximum load.An average of at least 3 specimens are reported.

TMA

Thermal Mechanical Analysis (Penetration Temperature) is conducted on 30mm diameter×3.3 mm thick, compression molded discs, formed at 180° C.and 10 MPa molding pressure for 5 minutes and then air quenched. Theinstrument used is a TMA 7, brand available from Perkin-Elmer. In thetest, a probe with 1.5 mm radius tip (P/N N519-0416) is applied to thesurface of the sample disc with 1N force. The temperature is raised at5° C./min from 25° C. The probe penetration distance is measured as afunction of temperature. The experiment ends when the probe haspenetrated 1 mm into the sample.

DMA

Dynamic Mechanical Analysis (DMA) is measured on compression moldeddisks formed in a hot press at 180° C. at 10 MPa pressure for 5 minutesand then water cooled in the press at 90° C./min. Testing is conductedusing an ARES controlled strain rheometer (TA instruments) equipped withdual cantilever fixtures for torsion testing.

A 1.5 mm plaque is pressed and cut in a bar of dimensions 32×12 mm. Thesample is clamped at both ends between fixtures separated by 10 mm (gripseparation ΔL) and subjected to successive temperature steps from −100°C. to 200° C. (5° C. per step). At each temperature the torsion modulusG′ is measured at an angular frequency of 10 rad/s, the strain amplitudebeing maintained between 0.1 percent and 4 percent to ensure that thetorque is sufficient and that the measurement remains in the linearregime.

An initial static force of 10 g is maintained (auto-tension mode) toprevent slack in the sample when thermal expansion occurs. As aconsequence, the grip separation ΔL increases with the temperature,particularly above the melting or softening point of the polymer sample.The test stops at the maximum temperature or when the gap between thefixtures reaches 65 mm.

Melt Index

Melt index, or I₂, is measured in accordance with ASTM D 1238, Condition190° C./2.16 kg. Melt index, or I₁₀ is also measured in accordance withASTM D 1238, Condition 190° C./10 kg.

ATREF

Analytical temperature rising elution fractionation (ATREF) analysis isconducted according to the method described in U.S. Pat. No. 4,798,081.The composition to be analyzed is dissolved in trichlorobenzene andallowed to crystallize in a column containing an inert support(stainless steel shot) by slowly reducing the temperature to 20° C. at acooling rate of 0.1° C./min. The column is equipped with an infrareddetector. An ATREF chromatogram curve is then generated by eluting thecrystallized polymer sample from the column by slowly increasing thetemperature of the eluting solvent (trichlorobenzene) from 20 to 120° C.at a rate of 1.5° C./min.

TREF

Large-scale TREF fractionation is carried by dissolving 15-20 g ofpolymer in 2 liters of 1,2,4-trichlorobenzene (TCB) by stirring for 4hours at 160° C. The polymer solution is forced by 15 psig (100 kPa)nitrogen onto a 3 inch by 4 foot (7.6 cm×12 cm) steel column packed witha 60:40 (v:v) mix of 30-40 mesh (600-425 μm) spherical, technicalquality glass beads (available from Potters Industries, HC 30 Box 20,Brownwood, Tex., 76801) and stainless steel, 0.028″ (0.7 mm) diametercut wire shot (available form Pellets, Inc. 63 Industrial Drive, NorthTonawanda, N.Y., 14120). The column is immersed in a thermallycontrolled oil jacket, set initially to 160° C. The column is firstcooled ballistically to 125° C., then slow cooled to 20° C. at 0.04° C.per minute and held for one hour. Fresh TCB is introduced at about 65ml/min while the temperature is increased at 0.167° C. per minute.

Approximately 2000 ml portions of eluant from the preparative TREFcolumn are collected in a 16 station, heated fraction collector. Thepolymer is concentrated in each fraction using a rotary evaporator untilabout 50 to 100 ml of the polymer solution remains. The concentratedsolutions are allowed to stand overnight before adding excess methanol,filtering, and rinsing (approx. 300-500 ml of methanol including thefinal rinse). The filtration step is performed on a 3 position vacuumassisted filtering station using 5.0 μm polytetrafluoroethylene coatedfilter paper (available from Osmonics Inc., Cat# Z50WP04750). Thefiltrated fractions are dried overnight in a vacuum oven at 60° C. andweighed on an analytical balance before further testing.

¹³C NMR Analysis

The samples are prepared by adding approximately 3 g of a 50/50 mixtureof tetrachloroethane-d²/orthodichlorobenzene to 0.4 g sample in a 10 mmNMR tube. The samples are dissolved and homogenized by heating the tubeand its contents to 150° C. The data is collected using a JEOL Eclipse™400 MHz spectrometer or a Varian Unity Plus™ 400 MHz spectrometer,corresponding to a ¹³C resonance frequency of 100.5 MHz. The data isacquired using 4000 transients per data file with a 6 second pulserepetition delay. To achieve minimum signal-to-noise for quantitativeanalysis, multiple data files are added together. The spectral width is25,000 Hz with a minimum file size of 32K data points. The samples areanalyzed at 130° C. in a 10 mm broad band probe. The comonomerincorporation is determined using Randall's triad method (Randall, JamesC.; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989)).

¹H NMR Analysis

Samples for Proton Nuclear Magnetic Resonance (¹H NMR) spectroscopy areprepared by adding approximately 3 g of d-1,1,2,2-tetrachloroethane(TCE) to 0.4 g sample in a 10 mm NMR tube. The samples are dissolved andhomogenized by heating the tube and its contents to 120° C. Completedissolution requires about 15 minutes. Occasionally, heating the sampleswith a heat gun is required for thorough homogenization. The sampletubes are visually inspected to ensure complete dissolution of thepolymer. Data are collected using a 300 MHz Varian NOVA Spectrometer.Thirty-two scans are collected at 120° C. The proton chemical shifts arereferenced against a residual proton signal from the TCE solvent at 7.26ppm.

FTIR

Fourier transform infrared spectroscopy (FTIR) is performed using aPerkinElmer Spectrum One spectrometer equipped with a UniversalAttenuated Total Reflectance (ATR) Sampling Accessory. A backgroundspectrum is obtained before each sample spectrum, and the crystalsurface sampling area is cleaned after each analysis. Each solid sampleis pressed against the crystal (internal reflectance element), and dataare collected using the following instrument parameters: 32 scans from650 to 4000 cm⁻¹ at 4 cm⁻¹ resolution. The data are analyzed usingSpectrum v5.0 software.

TEM

Samples for Transmission Electron Microscopy (TEM) are polished with adiamond knife using a Leica UC6:FC6 cryo-ultramicrotome at −100° C. andthen stained with RuO₄ vapors for 3 hours at room temperature.Thin-sections of approximately 90 nm thickness are collected at roomtemperature and examined with a JEOL JEM-1230 TEM running at anaccelerating voltage of 120 kV. Images are recorded digitally using aGatan Multiscan CCD camera, Model 749, and post processed with AdobePhotoshop CS2.

Atomic Force Microscopy (AFM)

Sections are collected from the sample material using a Leica UCT™microtome with a FC cryo-chamber operated at −80° C. A diamond knife isused to section all sample material to a thickness of 120 nm. Sectionsare placed on freshly cleaved mica surfaces, and mounted on standard AFMspecimen metal support disks with a double carbon tape. The sections areexamined with a DI NanoScope IV™ Multi Mode AFM, in tapping mode withphase detection. Nano-sensor tips are used in all experiments.

General Procedure: In the examples and comparative experiments thatfollow, unless otherwise noted, the reagent (i.e., starting polymers)are prepared as described hereinabove.

Example 1

A toluene solution containing 0.25 g each of a partially-hydrogenatedpolybutadiene (HPBD) and a partially-hydrogenated nitrile/butadienerubber (HNBR) is warmed to 95° C. and stirred at that temperature untilthe polymers are completely dissolved. To this stirred solution areadded 8 mg of Grubbs II metathesis catalyst. After 1 hour a product isprecipitated from the cooled solution by addition of methanol andrecovered by filtration. Removing volatile components from the isolatedsolids under reduced pressure gives 0.45 g of recovered product. SAXSanalysis of the recovered product shows phase separation of HPBD andHNBR polymer segments into microdomains, demonstrating the product is across-metathesized copolymer of HPBD and HNBR. A graph showing resultsat three temperatures is presented in FIG. 1. The peak observed at 300°C. is evidence of an ordered microphase morphology present in the liquidphase of the cross-metathesized copolymer product.

Comparative Experiment A

Example 1 is repeated using HPBD and HNBR reagent polymers, with theexception that no metathesis catalyst is used. Analysis of the recoveredproduct by SAXS shows it to be an isolated blend of the originalpolymers due to the fact that HPBD crystalline lamellae scatteringcontributions are evident at all temperatures less than the Tm of thecrystalline polymer within the range of 20 to 300° C. A graph of theSAXS curve at three temperatures within the range of the test is shownin FIG. 2. Failure to observe a peak at 300° C. indicates that theproduct of Comparative Experiment A shows no microphase order in theliquid phase, and thus the product of Comparative Experiment A isconsistent with a simple polymeric blend.

The SAXS results of FIGS. 1 and 2 indicate that block copolymers areprepared in the cross-metathesis reaction of Example 1, due to the factthat for the product of Example 1 scattering peaks for microphaseseparations of the incompatible polymer blocks, comprising chemicallydistinguishable polymer segments from the original unsaturated polymers,are observed at temperatures above the Tm of the crystalline polymerphase, notably, in the scattering pattern at 300° C. In the comparativeproduct of FIG. 2, the characteristic crystal X-ray pattern of theunaltered crystalline polymer (HPBD) is apparent below the Tm, and nomicrophase separation scattering peaks are detectable, demonstratingthat the product is merely a blend of the original polymers.

Example 2

A toluene solution containing 0.25 grams each of unsaturatedpoly(ethylene oxide) and 0.25 grams polyethylene-co-butadiene) is warmedto 105° C. and stirred at that temperature until the polymers aredissolved. To this stirred solution are added 9 milligrams of Grubbs IIcatalyst. After 1 hour, a polymer product is precipitated from thecooled solution by the addition of methanol and recovered by filtration.Removing volatile components from the isolated material under reducedpressure gives 0.47 grams of recovered polymer product. Tetrahydrofuran(30 ml) is added to the recovered product, which is placed on a shakerovernight to extract out non-metathesized unsaturated poly(ethyleneoxide). The polymer remaining after extraction is filtered, dried, andanalyzed by ¹H NMR spectroscopy as shown in FIG. 3 (lower spectrum).

Comparative Experiment B

Example 2 is repeated, with the exception that no metathesis catalyst isused with the results shown in FIG. 3 (upper spectrum). A comparison ofthe upper and lower spectra of FIG. 3 indicates that poly(ethyleneoxide) moieties are present in the polymer product of Example 2, but areabsent in the product of Comparative Experiment B. These results provideevidence for formation of a block copolymer in Example 2 throughmetathesis segment interchange reactions, but the same does not occur inComparative Experiment B.

Example 3

A toluene solution containing 0.25 g fumaryl-modified polycarbonate and0.25 g poly(ethylene-co-octene-co-butadiene) is warmed to 105° C. andstirred at that temperature until the polymers are completely dissolved.To this stirred solution are added 9 mg of Grubbs H metathesis catalyst.After 1 hour, a polymer product is precipitated from the cooled solutionby the addition of methanol, and the product is recovered by filtration.Removing volatile components under reduced pressure gives 0.47 g ofpolymer product. Analysis by TEM, as shown in FIG. 4, indicates anordered microphase morphology of the material. FIG. 5 shows SAXS data atthree temperatures. A peak at 300° C. demonstrates microphase order inthe liquid phase, as is also found in the non-liquid phases at 25° C.and 100° C. The data indicate formation of a block copolymer throughmetathesis segment interchange reactions.

Example 4

A toluene solution containing 0.10 g poly(ethylene-co-butadiene) and0.40 g poly(ethylene-co-octene-co-butadiene) is warmed to 105° C. andstirred at that temperature until the polymers are completely dissolved.To this stirred solution are added 8,000 ppm tungsten hexachloridecatalyst and 13,000 ppm tri-n-butylmethyltin co-catalyst. After 1 hour,a polymer product is precipitated from the cooled solution by theaddition of methanol and recovered by filtration. Removing volatilecomponents from the filtered product under reduced pressure gives 0.47 gof recovered polymer product, which is analyzed by crystallizationfractionation (CRYSTAF) as seen in FIG. 6.

Comparative Experiment C

Example 4 is repeated, with the exception that no metathesis catalyst isadded. The product recovered is analyzed by CRYSTAF as seen in FIG. 7.Significantly, in FIG. 7 a peak is observed at 80° C., which is notobserved in the CRYSTAF plot of FIG. 6. The peak at 80° C. is attributedto the presence of poly(ethylene-co-butadiene) polymer. The absence of apeak at 80° C. for the product of Example 4 (FIG. 6) indicates that thesolubility of this polymer product is increased as a result ofmetathesis segment interchange, thereby providing evidence for formationof a block copolymer. In contrast, the presence of a peak at 80° C. forthe comparative product of Comparative Experiment C (FIG. 7) indicatesthat this product is a simple blend of non-metathesized crystallinepolymer and poly(ethylene-co-octene-co-butadiene).

Example 5

A toluene solution containing 0.25 g each of poly(cyclooctadiene) andpartially-hydrogenated poly(nitrile-butadiene) rubber is warmed to 50°C. and stirred at that temperature until the polymers are completelydissolved. To this stirred solution is added 8.02 mg ofbenzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium. After one hour, the polymer productis precipitated from the cooled solution by the addition of methanol andrecovered by filtration. Volatile components are removed from theisolated solids under reduced pressure, leaving 0.39 g of a solidthermoplastic product. Analysis by SAXS, DSC and NMR showed the presenceof unsaturation but did not detect any crystalline polymer segments at atemperature above 30° C. in the metathesized copolymer product.

1. A process for preparing a cross-metathesized product mixturecomprising contacting a metathesis catalyst under metathesis conditionswith a composition comprising two or more chemically distinguishableethylenically unsaturated polymers, at least one of said ethylenicallyunsaturated polymers (first polymer) comprising internal unsaturationand having a molecular weight greater than 1,000, and having from 0.001to 50 mole percent unsaturation and at least one other of saidethylenically unsaturated polymers (second polymer) being an amorphouspolymer having a molecular weight greater than 1,000 and having anexpected Tg less than 0° C. and having from 0.001 to 5 mole percentinternal unsaturation, to thereby form the cross-metathesized reactionproduct.
 2. A process according to claim 1 wherein the first unsaturatedpolymer reagent comprises from 10 to 50 mole percent ethylenicunsaturation.
 3. A process according to claim 1 wherein the ethyleniccarbon content of the first unsaturated polymer reagent is less than orequal to 40 weight percent.
 4. A process according to claim 1 whereinthe first unsaturated polymer is a diene homopolymer or a copolymer ofone or more olefins with a diene, or a partially hydrogenated derivativethereof.
 5. A process according claim 1 wherein the second unsaturatedpolymer is a copolymer of ethylene, one or more C₃₋₂₀ α-olefins, and adiene or alkyne, or partially hydrogenated derivatives thereof.
 6. Aprocess according to claim 4 wherein the second unsaturated polymer is acopolymer of ethylene, one or more C₃₋₂₀ α-olefins, and a diene oralkyne, or a partially hydrogenated derivative thereof.
 7. A processaccording to claim 1 wherein the first unsaturated polymer ispolybutadiene, polyisoprene, poly(2-chloro-1,3-butadiene), orpoly(2-fluoro-1,3-butadiene) or a partially hydrogenated derivativethereof, and the second unsaturated polymer is a copolymer of ethylene,one or more C₃₋₈ α-olefins, and butadiene.
 8. A process according toclaim 3 wherein the first unsaturated polymer is polyisoprene,poly(2-chloro-1,3-butadiene), or poly(2-fluoro-1,3-butadiene) or apartially hydrogenated derivative of polybutadiene, polyisoprene,poly(2-chloro-1,3-butadiene), or poly(2-fluoro-1,3-butadiene), and thesecond unsaturated polymer is a copolymer of ethylene, one or more C₃₋₈α-olefins, and butadiene.
 9. A process according to claim 1 wherein thesecond unsaturated polymer is selected from the group consistingpartially hydrogenated nitrile butadiene rubber, poly(ethylene oxide),unsaturated polycarbonate, and poly(ethylene-co-octene -co-butadiene).10. A process according to claim 1 wherein the metathesis is conductedin the presence of a catalyst comprising (A) at least one organometalliccompound wherein the metal is selected from Groups 1, 2, 12 or 13 of thePeriodic Table of Elements, (B) at least one metal derivative whereinthe metal is selected from the group consisting of metals of Groups 5,6, or 7 of the Periodic Table of Elements, and, optionally, (C) at leastone chelating- or Lewis base-material.
 11. A process according to claim1 wherein the metathesis is conducted in the presence of a catalystcomprising a compound of the general formula:

wherein: M^(A) is ruthenium or osmium; X^(A) and X^(B) are the same ordifferent anionic ligand; L^(A) is a neutral electron donor ligand;L^(B) is a neutral electron donor ligand or a nitrogen containingheterocyclic carbene; and R^(A) and R^(B) are independently eachoccurrence hydrogen, or an alkyl, alkenyl, alkynyl, aryl, carboxylate,alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylthio,alkylsulfonyl, alkylsulfinyl, or silyl group of up to 20 atoms notcounting hydrogen, an alkyl, alkoxy, aryl, aralkyl, haloalkyl,haloalkoxy, haloaryl or haloalkaryl substituted derivative thereof; or afunctionalized derivative of any of the foregoing wherein the functionalgroup is hydroxyl, thiol, alcohol, sulfonic acid, phosphine, thioether,ketone, aldehyde, ester, ether, amine, imine, amide, imide, imido,nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide,carboalkoxy, carbamate, acetal, ketal, boronate, cyano, cyanohydrin,hydrazine, oxime, hydrazide, enamine, sulfone, sulfide, sulfenyl, orhalogen.
 12. A process according to claim 11 wherein the catalystcomprises a ruthenium derivative wherein L^(B) is a tertiary phosphine,and L^(A) is either a tertiary phosphine or a nitrogen containingheterocyclic ligand.
 13. A process according to claim 12 wherein L^(A)is an imidazolidinyl- or triazolyl- ligand of the formula:

wherein Ar independently each occurrence is an aryl group of up to 50atoms, and R^(C) independently each occurrence is hydrogen or an anionicligand group or multiple R^(C) groups collectively may form one or morefused rings.
 14. A cross-metathesized reaction product preparableaccording to claim
 1. 15. A cross-metathesized reaction productpreparable according to claim 14 wherein the expected Tg of the secondpolymer is less than −25° C.
 16. The cross-metathesized reaction productaccording to claim 14 wherein one polymer block comprises a partiallyhydrogenated polybutadiene and another polymer block comprises apartially hydrogenated butadiene nitrile rubber.
 17. Thecross-metathesized reaction product according to claim 14 wherein onepolymer block comprises a poly(ethylene oxide) and another polymer blockcomprises a poly(ethylene-co-butadiene).
 18. The cross-metathesizedreaction product according to claim 14 wherein one polymer blockcomprises a poly(ethylene-co-butadiene) and another polymer blockcomprises a poly(ethylene-co-octene-co-butadiene).
 19. Thecross-metathesized reaction product according to claim 14 wherein onepolymer block comprises an unsaturated polycarbonate and another polymerblock comprises a poly(ethylene-co-octene-co-butadiene).
 20. A partiallyhydrogenated derivative of a cross-metathesized reaction product ofclaim 14.